Electrically conductive polymer composition

ABSTRACT

New electrically conductive polymer compositions comprise 
     i) an electrically conductive polymer a) of one or more oxidatively polymerizable aromatic compounds and 
     ii) a polymer d) having ammonium, phosphonium or sulfonium groups in the polymer chain(s). 
     The polymer compositions comprising polymers a) and d) are prepared by oxidative polymerization of one or more aromatic compounds in the presence of a polymer b) having ammonium, phosphonium or sulfonium groups in the polymer chain(s) and containing a polydentate anionic complex which has a redox potential sufficient for enabling oxidative polymerization of the aromatic compounds. Said polymer b) which has a non-metallic anionic complex such as S 2  O 8   2-  is also novel.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation of application Ser. No. 08/052,203, filed Dec.17, 1992, now abandoned, which is a continuation-in-part of my U.S.patent application, Ser. No. 07/490,794, filed Mar. 8, 1990, now U.S.Pat. No. 5,788,766, which is a continuation-in-part of my abandoned U.S.patent application, Ser. No. 245,879, filed Sept. 16, 1988, abandoned.

BACKGROUND OF THE INVENTION

Electrically conductive polymers are the focus of considerable interestas they are possible replacements for metallic conductors orsemi-conductors in a wide variety of applications such as in batteries,in photovoltaics, and in electrostatic dissipation and electromagneticshielding uses.

Known methods of preparing electrically conductive polymers include anoxidative polymerization of aromatic compounds such as pyrrole oraniline.

The oxidative polymerization can be carried out electrochemically or bymeans of a chemical oxidizing agent. The electrically conductivepolymers are prepared in the form of powders, coatings or free-standingfilms.

It is also known to carry out the oxidative polymerization in thepresence of a carrier whereby an electrically conductive polymercomposition of the aromatic polymer and the carrier material isproduced. The known methods are discussed below in more detail.

It is well known that polypyrrole can be synthesized throughelectrochemical oxidative polymerization of pyrrole (A. F. Diarz et al.,J.C.S., Chem. Comm., 1979, pages 635 and 636). Unfortunately, themechanical properties of the produced polypyrrole coatings or films areoften unsatisfactory unless special care is taken to chose the propertype of solvents or conducting salts such as aromatic sulfonic,disulfonic or oligosulfonic acids disclosed in DE-A-34 21 296 andDE-A-33 18 857.

It is also known that pyrrole can be polymerized chemically, for examplewith potassium peroxydisulfate, potassium permanganate, sodiumperborate, iron(III) chloride or potassium bichromate in the absence orpresence of a conducting salt, (K. C. Khulbe and R. S. Mann, Journal ofPolymer Science, Vol. 20, pages 1089 et seq., 1982, S. P. Armes, Synth.Met., 20 (1987), pages 365-371, and DE-A-3325892). It is also known toproduce electrically conductive polyaniline powder through oxidativepolymerization using chemical oxidizing agents such as persulfate anions(J. C. Chiang et al., Synth. Met. 13 (1986), pages 193 et seq.

From DE-A-3307954 it is known that electrically conductive pyrrolepolymers having small particle sizes can be obtained by electrochemicalpolymerization of pyrrole in the presence of carriers of small size. Thecarriers contain acidic groups; exemplary of the carriers are sulfonatedpolystyrene and aluminum oxides.

GB-A-2 134 125 relates to the electropolymerization of pyrrole. A redoxspecies such as potassium ferricyanide can be additionally used.

In various scientific articles it has been suggested to prepareelectrically conductive polypyrrole particles by polymerizing pyrrole inan aqueous solution using FeCl₃ as an oxidizing agent in the presence ofdissolved methylcellulose, poly(vinyl pyrrolidone) poly(ethylene oxyide)or poly(vinyl-alcohol-co-acetate) which acts as a steric-stabilizer (S.P. Armes et al., J. Chem. Soc., Chem. Commun., 1987, pages 228-290 andR. B. Bjorklund et al., J. Chem. Soc., Chem. Commun., 1986, pages1293-1295).

DE-A-34 09 462 discloses electrically conductive thermoplastic mixturesof macromolecular compounds and polypyrrole having a small particlesize. The macromolecular compounds are polyolefins, styrenic polymers,vinyl chloride polymers, polyamides, polyesters, polyacetales orpolyethers. The thermoplastic mixtures are produced by treating asolution of the macromolecular compounds and pyrrole with an oxidizingagent, such as a peroxo acid or a salt thereof.

EP-A-0 229 992 relates to the oxidative polymerization of pyrrole,thiophene, aniline salts etc. with a chemical oxidizing agent such as aperborate, persulfate or percarbonate in the presence of a polymerhaving anionic surface character. This polymer is dispersed in thereaction medium, for example water, and acts as a polymeric counter-ionfor the polymer produced by oxidative polymerization. The polymer havinganionic surface character contains strong ionic groups, such as sulfateor sulfonate groups, in the polymer chain. EP-A-0 229 993 relates to theelectropolymerization of pyrrole in the presence of a polymer havinganionic surface character. This polymer is dispersed in the reactionmedium, for example water, and acts as a polymeric counter-ion for thepolymer produced by electrochemical oxidation. The same polymers havinganionic surface character are mentioned as in EP-A-0 229 92.

EP-A-0 104 726 discloses a polymer composition comprising anelectrically conductive polymer associated with a polymeric dopant whichstabilizes the polymer in an electrically conductive state. Negativelycharged dopants (counter-ions) are used for polypyrrole. These dopantshave negatively charged groups in the polymer chain(s). Exemplarythereof are ionizable polysulfonates or polycarboxylates. Theelectrically conductive polymer is produced by polymerizing acorresponding monomer in the presence of the polymeric dopant and anoxidizing agent. The oxidizing agent may be bonded to the polymericdopant. The ferric salt of a sulfonated polystyrene is suggested.

Although electrically conductive polymer compositions in powder form areuseful in several applications, for example as antistatic fillers forpolymers, it is often desirable to produce films or coatings from theelectrically conductive polymer compositions. DE-A-3227914 disclosespressing pyrrole polymers at a temperature between 150° C. and 300° C.and a pressure of at least 50 bar; however, this method is ratherinconvenient for preparing films or coatings.

Accordingly, others have suggested preparing composite films ofpolypyrrole and PVC, polyimides, polystyrenes and polymethacrylates (O.Niwa et al., J. Chem. Soc., Chem. Commun., 1984 pages 817 and 818; M.-A.De Paoli et al., J. Chem. Soc., Chem. Commun., 1984 pages 1015 and 1016and EP-A-191726). In Chemical Abstracts 106 (2):6150c providing anabstract of JP61/123638 it is suggested to soak a PVC film containinganiline with an ammonium persulfate solution. However, these methods arequite complicated and time consuming.

DE-A-3419788 discloses electrically conductive copolymers and blends ofpolymers which are composed of a polymer component A without aconjugated pi-system and a polymer component B with a conjugatedpi-system such as polypyrrole, polythiophene or polyaniline. Thedisclosed examples of component A are polyvinylchloride (PVC),polybutadiene, polyacrylate, polymethacrylate, copolymers of maleic acidanhydride and styrene, copolymers of butadiene and styrene,chloromethylated polystyrene or polymers which are functionalized with a--NH₂ or --OH group such as poly-(p-aminostyrene) or polyvinylaminewhich contain redox-active groups which have in the oxidized or reducedstate an active potential which is sufficient for oxidation or reductionof component B. As redox-active groups are disclosed complexes orchelates of transition metals, benzoquinone or ferrocene. Unfortunately,the polymer component A has to be functionalized in several steps inorder to incorporate the redox-active groups.

U.S. Pat. No. 4,604,427 discloses a method of impregnating a non-porous,swellable or soluble polyamide, polyvinyl chloride, polycarbonate,polyvinyl acetate or polyurethane with pyrrole or aniline and with achemical oxidant such as ammonium persulfate or iron trichloride.Powders or films are obtained.

U.S. Pat. No. 4,617,353 discloses a process wherein a solution of anelectrically non-conducting polymer such as PVC, butadiene copolymer oran olefin-homo- and copolymer is formed in a nonhydrous liquid reactionmedium and a pyrrole monomer is contacted in situ with a polymerizationinitiator selected from the group consisting of anhydrous halides ofiron, cobalt or nickel.

R. Yosomiya, Makromol. Chem., Rapid Commun. 7, pages 697 to 701 (1986)discloses that poly(vinyl alcohol), poly(methyl methacrylate) andpoly(vinyl chloride) are dissolved in an appropriate solvent togetherwith CuCl₂ or FeCl₃, the solution is cast on a glass plate and dried toform a film which is then reacted with pyrrole.

Unfortunately, the oxidant or polymerization initiator is inhomogenouslydistributed in the films prepared according to these processes and themechanical properties of the films are often insufficient.

P. Aldebert et al., J. Chem. Soc., Chem Commun., 1986, pages 1636 to1638 disclose polymer alloys with mixed electronic and ionicconductivity which have been synthesized from perfluorosulfonatedionomer membranes and monomer precursors of electronically conductingpolypyrrole or polyaniline. A commercially available solid acidic Nafion(Trademark) film is soaked in an aqueous solution containing 2MFe(ClO₄)₃ and 0.5 M HClO₄. The proton sites of the Nafion film areexchanged by iron(III) ions. The Nafion film is produced from anionomeric polymer containing SO₃ group. Polymerization of aniline insidethe ionic membrane is obtained by soaking the Fe³⁺ exchanged Nafion in a1M aqueous solution of aniline acidified with H₂ SO₄ or HClO₄.

Due to the interesting properties and the variety of applications of theelectrically conductive pyrrole or aniline polymer compositions and dueto the limited choice of oxidizing agents and processes which are usefulfor producing electrically conductive pyrrole or aniline polymers in theform of a film or coating, it remains desirable to provide a newelectrically conductive polymer composition comprising polypyrrole,polythiophene, polyaniline or similar polymers which polymer compositioncan be produced in the form of a film or a coating but also in the formof a powder or granules. Furthermore, it remains desirable to provide anew oxidizing agent and a new process useful for producing suchelectrically conductive polymer composition.

Surprisingly, it has been found that certain types of polymericoxidizing agents are useful in the oxidative polymerization of aniline,pyrrole and other aromatic compounds and that the reduced form of theoxidizing agent forms a portion of the electrically conductive polymercomposition.

SUMMARY OF THE INVENTION

Accordingly, one aspect of the present invention is an electricallyconductive polymer composition comprising

i) an electrically conductive polymer a) of one or more oxidativelypolymerizable aromatic compounds and

ii) a polymer d) having ammonium, phosphonium or sulfonium groups in thepolymer chain(s).

The above-mentioned electrically conductive polymer composition isproduced by oxidative polymerization of one or more aromatic compoundsin the presence of a polymer b) having ammonium, phosphonium orsulfonium groups in the polymer chain(s) and containing a polydentate,anionic complex which has a redox potential sufficient for enablingoxidative polymerization of said aromatic compound(s).

Another aspect of the present invention is a polymer having ammonium,phosphonium or sulfonium groups in the polymer chain(s) which polymer iscross-linked via polydentate, anionic non-metallic complexes which havea redox potential sufficient for enabling oxidative polymerization ofpyrroles, thiophenes or anilines.

The above-mentioned electrically conductive polymer composition of thepresent invention is useful in an electrical conductor orsemi-conductor, an electrode material, a plastic material or a paperprovided with an antistatic finishing, an electromagnetic shieldingmaterial, an electrical cell, a heating element or an electrochemicalmembrane.

Yet another aspect of the present invention is a polymer containing theabove-mentioned electrically conductive polymer composition in powderform as an antistatic filler.

DETAILED DESCRIPTION OF THE INVENTION

The electrically conductive polymer composition of the present inventioncomprises

i) an electrically conductive polymer a) containing one or moreoxidatively polymerizable aromatic compounds in polymerized form and

ii) a polymer d) having ammonium, phosphonium or sulfonium groups in thepolymer chain(s).

The electrically conductive polymer composition is produced by oxidativepolymerization of the aromatic compound(s) in the presence of a polymerb) containing a polydentate anionic complex which has a redox potentialsufficient for enabling oxidative polymerization of the aromaticcompound(s). Polymer b) has the same ammonium, phosphonium or sulfoniumgroups in the polymer chain(s) as polymer d).

Polymer b) is described in the following paragraphs in detail. Thepolydentate anionic complexes which have a redox potential sufficientfor enabling oxidative polymerization of the aromatic compounds may bemetallic complexes such as MnO₄ --, Cr₂ O₇ ² -- or [Fe(CN)₆ ]³ --.However, non-metallic complexes are preferred, typically those whereinthe following elements are the main elements of the complex: elements ofgroup IIIA, such as boron, of group VA, such as nitrogen or phosphorous,or of group VIA, such as oxygen or sulfur, of the Periodic Table ofElements. Exemplary thereof are S₂ O₈ ² --, B₄ O₇ ² -- and ClO₄ --, withS₂ O₈ ² -- being the most preferred complex.

The non-metallic polydentate anionic complexes are preferred over thepolydentate anionic metal complexes. For example, unlike complexescontaining heavy metal ions, they are not subject to ecologicaldiscussions.

Polymers which are cross-linked with polydentate, anionic metalliccomplexes are known. From E. A. Bekturov, "Interaction ofpoly(diallyldimethylammonium chloride) with ferro- and ferricyanideanions", Macromol Chem 186/71-75 (1986) and DD-A-147 949 it is known toreact a poly(diallyldialkylammonium chloride) with metallic complexessuch as MnO₄ -- or Fe(CN)₆ ³ --. In DD-A-147 949 it is suggested to makeuse of this reaction in waste water treatment. However, the usefulnessof such polymers being cross-linked with polydentate, anionic metalcomplexes for preparing electrically conductive polymer compositionsaccording to the processes of the present invention is not known.

The standard half cell potential of the polydentate anionic redox systemis preferably more than +0.1 Volt, more preferably more than +0.8 Volt,most preferably more than +1.2 Volt, depending on the type of thearomatic compound(s) to be polymerized, i.e. on the type of monomericprecursor(s) of polymer a). It is important that the anion not only hasa redox potential sufficient for enabling oxidative polymerization ofthe monomeric precursor(s) of polymer a) but that it is also apolydentate complex. The expression "polydentate complexes" includesbidentate, tridentate, etc. complexes. The anionic complexes are mono-or polyvalent, preferably mono- to trivalent, more preferably divalent.Most preferably, polymer b) contains anionic polynuclear complexes whichcontain several coordination centers linked together with bridge ligandsor metal to metal bonds. The polydentate anionic complexes causecross-linking of the polymer.

Depending on the way of producing polymer b) it can be obtained in theform of a film or a coating if it contains these polydentate anioniccomplexes. Without wanting to be bound to a particular theory, it isbelieved that the polydentate anionic complexes cause cross-linking ofthe polymer whereby films or coatings are obtained. As described furtherbelow, the polymer b) can also be obtained in the form of a powder whichhas an average particle size of 5 nm to 1 mm, generally of 10 nm to 0.1mm, preferably of 100 nm to 0.1 mm and more preferably of 500 nm to 0.01mm.

Polymers b) which are cross-linked via the above mentioned non-metalliccomplexes such as S₂ O₈ ² -- or ClO₄ -- are novel and are one aspect ofthe present invention.

Polymer b) has phosphonium or sulfonium groups or, preferably, ammoniumgroups in the polymer chain(s). These groups may be located in the mainchain and/or in the side chain(s) of the polymer. By the term "a polymerb) having phosphonium, sulfonium or ammonium groups" are also meantpolymers which have phosphonium and sulfonium groups or phosphonium andammonium groups or sulfonium and ammonium groups or phosphonium,sulfonium and ammonium groups.

The polymers b) can be prepared from known water-soluble polymers c)which contain the same ammonium, phosphonium or sulfonium groups aspolymer b) but which contain monodentate anions, for example hydroxyl,halogen such as bromide, fluoride or chloride ions, tetraflouroborate,phosphate, nitrate, sulfate, HSO₄ -- or organic anions, such as acetateor the anion of benzene sulfonic acid or p-styrene sulfonic acid, byexchanging these monodentate anions with polydentate anionic complexeshaving the desired redox potential such as S₂ O₈ ² --, ClO₄ --, Cr₂ O₇ ²--, MnO₄ -- or [Fe(CN)₆ ]³ -- and cross-linking the polymer. The anionexchange however does not occur when the polydentate anionic complexessuch as S₂ O₈ ² -- are contacted with a monomeric precursor of polymerb).

Preferred ammonium, phosphonium and sulfonium groups in polymers b) andc) are ##STR1##

wherein R₁ and R₂ independently are hydrogen, alkyl, such as a C₁₋₆-alkyl, preferably methyl, ethyl, the propyl, butyl, pentyl or hexylgroups, for example n-propyl or isopropyl, primary, secondary ortertiary butyl, neopentyl or n-hexyl, aralkyl, such as benzyl, or phenylor wherein R₁ and R₂ are joined together to represent the atoms requiredto complete a heterocyclic ring, such as piperidine, pyrrolidine, ormorpholine, e.g. --(CH₂)₅ --,--(CH₂)₄ --, or --(CH₂)₂ O(CH₂)₂ --

and wherein R₃ and R₄ independently are alkyl, such as a C₁₋₆ -alkyl,preferably methyl, ethyl, the propyl, butyl, pentyl or hexyl groups, forexample n-propyl or isopropyl, primary, secondary or tertiary butyl,neopentyl or n-hexyl, monocyclic aryl, such as phenyl, or monocyclicaryl-alkyl, such as benzyl and wherein R₅ is alkyl, such as a C₁₋₆-alkyl, preferably methyl, ethyl, the propyl, butyl, pentyl or hexylgroups, for example n-propyl or isopropyl, primary, secondary ortertiary butyl, neopentyl or n-hexyl, or monocyclic aryl-alkyl, such asbenzyl.

If R₁, R₂, R₃, R₄ and/or R₅ is or contains an alkyl radical, the alkylradical preferably is methyl or ethyl.

The radicals R₁, R₂, R₃, R₄ and/or R₅ should be chosen in such a mannerthat polymer c) is soluble in water to a substantial extent.

The preferred polymers b) and c) are homo- or copolymers produced fromone or more monomers of Formula ##STR2##

wherein

A and B are the same or different and represent a C₁₋₁₂ -alkyl or phenylradical, the C₁₋₁₂ -alkyl or phenyl radical can be unsubstituted orsubstituted with a substituent which is not polymerizable in thepresence of a free radical initiator; or A and B together represent--CH₂ --CH₂ --, --CH(CH₃)--CH(CH₃)--, --CH═CH--CH═CH--, --CH═CH--CH═N--,or --CH═CH--N═CH--; and

R and R' are the same or different and represent hydrogen, nitro-C₁₋₆--alkyl, C₁₋₆ --alkyl or phenyl radicals, the alkyl or phenyl radicalsare optionally substituted by hydroxy, amido, loweralkoxy, phenoxy,naphthoxy, cyano, thioloweralkoxy, thiophenoxy, loweralkoyl or 5- or6-membered cycloalkyl and which polymers b) and c) contain the abovementioned anions.

Preferred substituted C₁₋₁₂ -alkyl or phenyl radicals A or B eachindependently are substituted by hydroxy, amido, loweralkoxy, phenoxy,naphthoxy, cyano, thioloweralkoxy, thiophenoxy, loweralkoyl, 5- or6-membered cycloalkyl, or represent a nitro substituted C-₁₋₁₂ -alkylgroup. The alkyl groups A and B each independently have 1 to 12,preferably 1 to 8 carbon atoms, such as, for example, methyl, ethyl,propyl, isopropyl, n-, s- or t-butyl, pentyl, 2-ethyl-hexyl, octyl ordodecyl groups. Preferably, lower alkyl groups A and B when they aresubstituted, each independently represent hydroxymethyl, hydroxyethyl orethoxyethyl groups. Preferably, unsubstituted lower alkyl groups A and Beach independently are methyl or ethyl.

Suitable groups R and R' independently are hydrogen, C₁₋₆ -alkyl,preferably methyl, ethyl, the propyl, butyl, pentyl or hexyl groups, forexample n-propyl or isopropyl, primary, secondary or tertiary butyl,neopentyl or n-hexyl, or phenyl radicals, the alkyl or phenyl radicalsare optionally substituted by the groups indicated above.

Preferably R and R' each independently represent C₁₋₆ -alkyl, morepreferably methyl or ethyl, or hydrogen.

"Lower" alkyl, alkoyl or alkoxy means alkyl, alkoyl or alkoxy groupshaving from 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms, such asmethyl, ethyl, methanoyl, ethanoyl, methoxy or ethoxy.

The most preferred polymers b) are homo- or copolymers of one or moremonomers of formula I wherein A and B each independently representmethyl, ethyl or unsubstituted phenyl, preferably methyl; and R and R'independently are hydrogen or methyl, and which polymers arecross-linked with S₂ O₈ ² -- anions.

Further useful polymers b) are homo- or copolymers of one or moremonomers of formula II ##STR3##

which polymers are cross-linked with anions of the above mentionedtypes, and A, B and R have the above mentioned meanings and R₁₂represents hydrogen or has one of the meanings stated for A.

The monomers of formula I or II can also be copolymerized with minoramounts of any other monomer copolymerizable therewith, for example withacrylonitrile, styrene, acrylamide or vinyl acetate. Such other monomerspreferably are used in an amount of less than 50 percent, morepreferably up to 20 percent, most preferably up to 10 percent, based onthe total weight of the polymer. If such other monomers are used, theiramounts should be chosen in such a manner that polymer c), containingmonodentate anions, such as hydroxyl or chloride, is water-soluble.

Further useful polymers b) are the polymers disclosed in U.S. Pat. Nos.3,401,152 and 3,706,677 which contain sulfonium groups, for example poly(p-xylylene-α-dimethylsulfonium chloride), polymeric p-phenylenedimethylene bis(dimethyl sulfonium chloride), polymeric2,5-dimethyl-p-phenylene dimethylene bis(diethyl sulfonium chloride),polymeric p-phenylene dimethylene bis (diethyl sulfonium chloride) andpolymeric p-phenylene dimethylene bis (di-n-butylsulfonium chloride).

Specific examples of known polymers c) which are useful for preparingthe cross-linked polymer b) are poly(dimethylammoniono)-1,6-hexylenebromide, poly(2-acryloxyethyl-dimethylsulfonium chloride),poly(glycidyltributyl phosphonium chloride), poly(acryloxyethyltrimethyl ammonium chloride), poly(methacryloxyethyl trimethyl ammoniumchloride), poly(vinyl benzyltrimethyl ammonium chloride),poly(methyl(vinyl pyridinium)-ammonium chloride),poly(3-methacryloxyl(2-hydroxy-propyl)trimethyl ammonium chloride),poly(3-acrylamido-3-methyl-butyl trimethyl ammonium chloride),poly(alpha-(methylene trimethyl ammonium chloride)-ethylene oxide),poly(dimethyl propyl ammonium chloride), quaternized poly(2- or4-vinylpyridine), quaternized polyethyleneimine, poly(vinyl methylpyridinium chloride) or quaternized poly(dimethylaminoethylmethacrylate) or copolymers of the monomeric precursors of the abovementioned polymers with vinyl monomers, in particular copolymers ofvinylpyridine/styrene, vinylpyridine/butadiene,vinylpyridine/styrene/butadiene-terpolymers, the vinylpyridine-moitiesbeing converted into their salt form by treatment with acids, preferablyinorganic acids or being in their quaternized form. Terpolymers havingpoly(vinylbenzyltrimethylammonium chloride)/ styrene/butadiene units orterpolymers having poly(acryloxyethyltrimethyl ammonium chloride) orpoly(methacryloxyethyltrimethyl ammonium chloride) units instead ofpoly(vinylbenzyltrimethyl ammonium chloride) are also useful. The mostpreferred copolymers or terpolymers are those having the moities such asthe quaternized vinylpyridine or vinylbenzyltrimethyl ammonium chloridein an amount of 1 to 50 percent and butadiene in an amount of 20 to 70percent, based on the polymer weight, any remaining polymer portionbeing copolymerized styrene. Mixtures of a polymer C), preferably of apoly(diallyldialkyl ammonium halide) with a polymer dispersion are alsouseful for preparing the electrically conductive polymer composition ofthe present invention and are also included in the definition of "thepolymer c)". Preferred polymer dispersions are known aqueous dispersionsof the polystyrene, polystyrene/butadiene or carboxylatedpolystyrene/butadiene type which are generally known as adhesives orpigment binders. The mixtures preferably contain from 1 to 50 percent,more preferably from 10 to 40 weight percent of the polymer c).

The polymers c) having cationic groups of the type disclosed above andhaving monodentate anions are known in the art. The polymers c) are forexample described in U.S. Pat. Nos. 2,923,701 and 3,968,037 and inBritish patents 1,037,028 and 1,084,540 and in Belgium patent 664427.These known polymers are typically linear and usually soluble orswellable in water to a substantial extent. They can be producedaccording to known polymerization processes in aqueous solution oraccording to emulsion or suspension polymerization. Solutionpolymerization is described in U.S. Pat. No. 3,288,770. Emulsionpolymerization and suspension polymerization are described in U.S. Pat.Nos. 3,284,393 and 2,982,749. From published Dutch patent application6505750 radical-type polymerization of diallyldimethylammonium chloridein the presence of a persulfate catalyst is known. However, theradical-type polymerization does not provide cross-linked polymerscontaining persulfate anions.

As mentioned above, the polymers c) are preferably linear. However, itis also possible to start from known polymers of the above mentionedtypes which have been cross-linked with difunctional or trifunctionalnon-ionic monomers, for example diallylamine, triallylamine,divinylpyridine, ethylene glycol diacrylate, divinylbenzene,diallylphthalate, diallylfumarate or trivinylbenzene. These products canbe slightly cross-linked and still substantially water-soluble. Thepolymers c) can contain up to 15 weight percent of the monomericprecursor. However polymers c) preferably contain less than 5 weightpercent, more preferably less than 0.2 weight percent.

The polymer c) used for preparing polymer b) by anion exchange andcross-linking should generally have a weight average molecular weightM_(n) of more than 20,000, preferably from 50,000 to 5,000,000 and morepreferably from 200,000 to 1,500,000.

A suitable polymer b) containing polydentate anionic complexes can beproduced by exchanging at least a portion of the anions in a knownpolymer c) described above with the polydentate anionic complexesdescribed above, S₂ O₈ ² -- being the most preferred one. When thepolydentate anionic complex is a permanganate anion, for example in theform of an aqueous potassium permanganate solution, such aqueoussolutions preferably contain traces of an acid.

The following description of the preparation of polymer b) isillustrated using the S₂ O₈ ² -(peroxodisulfate) anion although theuseful types of anions are not restricted thereto.

In the practice of preparing polymer b), the water-soluble polymer c) ispreferably reacted with peroxodisulfuric acid or a peroxodisulfate saltat a temperature of from about -20° C. to about +40° C., preferably fromabout -20° C. to about +25° C., more preferably at about ambienttemperature. For the ionic cross-linking with peroxodisulphate,solutions of peroxodisulphuric acid or its ammonium, alkali or alkalineearth metal salts, for example the tetrabutylammonium, sodium orpotassium salts, are preferred. The acid or the salt may be dissolved inan organic solvent but an aqueous solution is preferred. Theconcentration of peroxodisulfuric acid or a salt thereof is not verycritical. It can be in the range of from about 0.01 weight percent,preferably of from about 0.1 weight percent up to a saturated aqueoussolution. Polymer b) can either be produced in the form of a film or acoating as described in methods A to D below or in the form of a powderor granules as described in methods E to H below.

In a first method A for producing a polymer b), a solution of anabove-mentioned known polymer c) which typically contains monodentateanions such as halogen, preferably chlorine, is applied to a substratesuch as a glass plate. Aqueous solutions which contain from 0.1 to 25weight percent of polymer c), more preferably from 1 to 20 weightpercent of polymer c), most preferably from 1 to 10 weight percent ofpolymer c) are preferred. Solutions of polymer c) in an organic solventare less preferred. The solution of polymer c) and the substrate arethen dipped into an above described solution which containsperoxodisulphate ions. The solution of polymer c) can, for example, besimply poured on a glass plate which is then dipped into the solutioncontaining peroxodisulphate ions. An aqueous solution containing about 5to about 20 weight percent of Na₂ S₂ O₈ is preferred. The anion exchangebetween the monodentate anion, such as chloride, and theperoxodisulphate ion and the cross-linking usually take place within acouple of minutes. The polymer b) containing peroxodisulphate ions isdeposited on the substrate in the form of a solid, water-insoluble film.

In a further method B, a film produced from a known above describedpolymer c) is dipped into the above described solution containingperoxodisulphate ions. An aqueous solution containing about 5 to about20 weight percent of Na₂ S₂ O₈ is preferred. The film of the polymer c)can be produced by evaporating corresponding solutions of polymer c)which are preferably in contact with a substrate such as a glass plate.This method is particularly useful when employing the above mentionedcross-linked polymeric starting materials c). The ion exchange andcross-linking reaction typically takes up to about two hours for filmshaving a thickness of up to about 0.5 mm.

Films of polymer b) can also be produced according to a process C whichis analogous to the process described in U.S. Pat. No. 3,276,598. Inthis process aqueous solutions of the polymeric starting material c) andof the peroxodisulphate ion are placed in two chambers which areseparated from each other with a filter paper or another material havingfine pores. This method is particularly suitable for producing very thinfilms of less than 0.1 mm. Solutions containing from 0.1 to 25, morepreferably from 0.5 to 5 weight percent of polymer c) and solutionscontaining from 0.1 to 70, more preferably from 1 to 20 weight percentof a peroxodisulphate salt are preferred.

In a further method D, the above mentioned film of the known polymer c)is Sprayed with the above described aqueous solutions containingperoxodisulphate ions. An aqueous solution containing about 5 to about20 weight percent of Na₂ S₂ O₈ is preferred.

In a further method E, a solution of the known polymer c) is added dropby drop to the above-mentioned peroxodisulphate solution. The polymericsolution preferably contains from about 0.1 to about 25 weight percent,more preferably from about 0.5 to about 10 weight percent of polymer c).The peroxodisulphate solution preferably comprises from about 0.1 toabout 70 weight percent, more preferably from about 0.5 to about 20weight percent of a peroxodisulphate salt. Granules are obtained whichcan be ground to a powder if desired.

A further method F involves suspending a known solid polymer c) in aperoxodisulphate solution. This method is particularly useful forpolymers produced according to suspension polymerization and forpolymers which have been cross-linked with a multivalent nonionicmonomer of the above mentioned type.

According to the following methods G and H, polymer b) is obtained inthe form of fine particles by reacting a polymer c) and peroxodisulphateions in an aqueous solution. The produced particles of polymer b) havean average size of 5 nm to 1 mm, generally of 10 nm to 0.1 mm,preferably of 100 nm to 0.1 mm and more preferably of 500 nm to 0.01 mm.The concentration of the water-soluble polymer c) in the aqueoussolution is critical for obtaining a cross-linked polymer b) in the formof fine particles having the above-mentioned size. Polymer c) shouldgenerally be dissolved in water in a concentration of 0.01 to 5 percent,preferably of 0.5 to 2 percent, based on the weight of the aqueoussolution. If the concentration of polymer c) is too high, the producedwater-insoluble polymer b) precipitates from the solution in relativelylarge flocs. Polymer c) can be added to an aqueous solution of theperoxodisulfuric acid or a salt thereof or vice versa. Generally thesolution is stirred during the addition, preferably at 300 rpm or more,more preferably at 400 rpm to 600 rpm (revolutions per minute).

According to method G of producing polymer b), the molar ratio betweenthe ammonium, phosphonium or sulfonium groups in polymer c) and theperoxydisulfate ions is 2:1 or more, preferably from 2:1 to 2.5:1. Thecross-linked polymer b) containing S₂ O₈ ² -- groups is then produced inthe form of fine, white particles. The liquid phase of the aqueousdispersion containing the fine particles of the water-insoluble polymerb) does not contain substantial amounts of peroxodisulfate anionsanymore, typically less than 3 percent, in many cases even less than 1percent, of the original amount of dissolved peroxodisulfate anions. Theproduced aqueous dispersion of polymer b) can be directly used forproducing the electrically conductive polymer a) as described below. Thedirect use of the aqueous dispersion is particularly useful whenpreparing polymer b) in the form of very fine particles which can not beseparated from the water anymore. When polymer b) is obtained in largerparticles, it can be separated from the water if desired, for example byfiltration.

According to method H of producing polymer b), the molar ratio betweenthe ammonium, phosphonium or sulfonium groups in polymer c) and theperoxydisulfate ions is less than 2:1, preferably from 0.001:1 to1.98:1, more preferably from 0.01:1 to 1.9:1, most preferably from 0.2:1to 1.5:1. The produced waterinsoluble polymer b) in the form of fine,white particles can be separated from the water, for example byfiltration.

The polymer b) produced according to method E to H above can be washed,for example with water and/or methanol, and dried, for example undervacuum at 20° to 35° C., preferably at ambient temperature The producedpolymer b) is cross-linked with S₂ O₈ ² -- groups at a molar ratio ofcationic groups, such as ammonium, sulfonium or phosphonium groups, toS₂ O₈ ² -- groups of 2:1.

According to the above described methods A to H, polymers b) areobtained in which more than 50 percent, preferably more than 80 percentand more preferably more than 95 percent of the total anion content arethe above described polydentate anionic complexes depending, amongothers, on the concentration of the salt solutions comprising theseanions in methods A to H.

In some eases it is useful to carry out the process for producingpolymer b) in an aqueous solution wherein conducting salts aredissolved. Conducting salts are generally known. Preferred salts arealkali or ammonium salts which have anions of the following type: BF₄⁻⁻, PF₆ ⁻⁻, AsF₆ ⁻⁻, SbCl₆ ⁻⁻, ClO₄ ⁻⁻, IO₄ ⁻⁻, HSO₄ ⁻⁻, SO₄ ²⁻⁻, CF₃SO₃ ¹³ , CH₃ C₆ H₄ SO₃ ⁻⁻, CF₃ COO⁻⁻, HC₂ O₄ ⁻⁻, ZrF₆ ²⁻⁻, TiF₆ ²⁻⁻,C₁₋₁₂ -alkylsulfate, C₁₋₁₂ -alkylsulfonate, C₁₋₁₂ -alkylphosphate orC₁₋₁₂ -alkylphosphonate.

The aqueous solution preferably contains the conducting salt in anamount of from 0.001 to 10 mols per liter, more preferably from 0.01 to1 mol per liter. Preferred cations are sodium, potassium, ammonium ortetrabutylammonium ions. Instead of the salts, acids such as sulphuricacid are also useful. A preferred type of aqueous solution are mixturesof water and methanol containing the above mentioned salts.

Polymer b) is a solid oxidizing agent for carrying out the oxidativepolymerization of aromatic compounds according to the processesdescribed below wherein the electrically conductive polymer compositionsof the present invention are produced.

Polymer compositions are obtained which contain the electricallyconductive polymer a) and a polymer d) having ammonium, phosphonium orsulfonium groups in the polymer chain(s). The polymer d) is the reducedform of polymer b) (which has been used as an oxidizing agent). Polymerd) contains the same ammonium, sulfonium or phosphonium groups in thepolymer chain(s) as polymer b) and the reduced form of the polydentate,anionic complexes. If polymer b) contains S₂ O₈ ²⁻⁻ complexes, polymerd) contains sulfate groups.

Typical examples of a polymer a) having one or more aromatic compoundsin polymerized form are polymers containing aromatic rings, furane,aniline, pyrrole and/or thiophene units, such as substituted ornon-substituted polypyrroles, substituted or non-substitutedpolythiophenes, substituted or non-substituted polyanilines orsubstituted or non-substituted polyphenylenes. The polypyrroles and inparticular the polyanilines are preferred.

The expression polypyrrole used herein means homo- or copolymers ofpyrrole and/or substituted pyrrole or copolymers of pyrrole andheteroaromatic compounds having rings of 5 or 6 members.

Preferred pyrroles which can be polymerized according to oxidativepolymerization are represented by formula IV. ##STR4##

wherein

R¹⁶ is alkyl, cycloalkyl, aryl, aralkyl, or alkaryl, which groups areoptionally substituted by --COR²⁰, --COOR²⁰, --SO₂ R²⁰, --SO₃ R²⁰, --PO₃R²⁰ R²¹, --PO₂ R²⁰, --NR²⁰ R²¹, --OR²⁰, --SR²⁰, --CN or --SiR²⁰ R²³ R²⁴.

or R¹⁶ is hydrogen, --CN, --SO₂ R²⁰, --SO₃ R²⁰, --COR²⁰, --PO₂ R²⁰ or--Si(R²²)₃ ;

R²⁰ and R²¹ independently represent hydrogen, alkyl, aryl or aralkyl;

R²², R²³ and R²⁴ independently represent alkyl or phenyl;

R¹⁷ and R¹⁸ independently represent hydrogen, alkyl, cycloalkyl, aryl,aralkyl, alkaryl, --COR19, --CN or halogen; and

R¹⁹ is hydrogen, alkyl or aryl.

Among the alkyl radicals, C₁ -C₂₀ -alkyl groups are preferred, such asmethyl, ethyl, propyl, butyl, cetyl, lauryl or stearyl groups. Methyl isthe most preferred alkyl radical.

Among the cycloalkyl radicals, a C₅ -C₇ -cycloalkyl is preferred, thatis cyclopentyl, cyclohexyl or cycloheptyl, of which cyclohexyl is themost preferred.

Preferred halogen radicals are bromine and chlorine. Aryl radicalspreferably represent phenyl or naphthyl, most preferably phenyl.

Aralkyl preferably represents a C₇ -C₁₄ -aralkyl, most preferablybenzyl.

Substituted groups are preferably mono- or disubstituted, mostpreferably mono-substituted. Pyrroles which are substituted at thearomatic ring are preferably substituted in the 3- and/or 4-position.

Preferred pyrroles are the unsubstituted pyrrole, the N-alkylpyrroles,in particular the N-methylpyrrole, or the N-arylpyrroles, in particularthe N-phenylpyrrole as well as the pyrroles which are substituted at thearomatic ring with one or two alkyl groups, preferably methyl groups orone or two halogen radicals, preferably bromine or chlorine.

The optionally substituted pyrroles can be copolymerized with otherheteroaromatic compounds, preferably with furane, thiophene, thiazole,oxazole, thiadiazole, imidazole, pyridine, 3,5-dimethylpyridine,pyrazine, pyridazine, 3,5-dimethylpyrazine, carbazole or phenothiazine.

The most preferred pyrrole copolymers are those produced fromunsubstituted pyrrole and optionally substituted N-methylpyrrole andcopolymers produced from unsubstituted pyrrole or N-methylpyrrole andfurane or thiophene. These pyrrole copolymers contain preferably fromabout 0.1 to 10 mol percent of the aforementioned other heteroaromaticcompounds, based on the amount of pyrrole. The most preferredpolypyrrole is a homopolymer of unsubstituted pyrrole.

"Polyaniline" includes homo- or copolymers of aniline and/or substitutedaniline or copolymers of aniline and/or substituted aniline withheteroaromatic compounds having five our six members in the aromaticring. Substituted anilines are preferably substituted in the meta- orortho-position. Preferred monomers for producing a polyaniline areunsubstituted aniline, methylanilines, such as N-methylaniline,2-methylaniline or 3-methylaniline, methoxyanilines, such as 3-methoxy-or 2-methoxyaniline, and N-phenyl-1,4-diaminobenzene. Preferred anilinecopolymers are produced from substituted or, preferably, unsubstitutedaniline and up to 25 percent pyrrole, based on the total polymer weight.Other preferred aniline copolymers contain unsubstituted aniline and upto 50 percent, preferably up to 25 percent, of an above-mentionedsubstituted aniline, such as 3-methoxy- or 2-methoxyaniline, based onthe total polymer weight. A homopolymer of unsubstituted aniline ispreferred.

Polythiophene includes homo- or copolymers of thiophene and/or asubstituted thiophene or copolymers of thiophene and/or a substitutedthiophene with heteroaromatic compounds having 5 or 6 members in thearomatic ring. Preferred thiophene monomers are the unsubstitutedthiophene or thiophene which is substituted at the 3-position, such asthiophene-3-sulfonic acid.

The electrically conductive polymer composition, comprising theabove-mentioned polymers a) and d) can be produced by polymerizing

I) one or more aromatic compounds, i.e. the monomeric precursor(s) ofpolymer a), which are dissolved or dispersed in an aqueous or organicsolvent in the presence of a film or coating of polymer b) describedabove or

II) one or more aromatic compounds in the gas phase in the presence of afilm or coating of polymer b) described above or

III) one or more aromatic compounds which are dissolved or dispersed inan aqueous solvent in the presence of a polymer b) in the form of fineparticles described above or

IV) one or more aromatic compounds which are dissolved or dispersed inan aqueous solvent in the presence of an above-mentioned water-solublepolymer c) and a water-soluble oxidizing agent containing a polydentateanionic complex having a redox potential sufficient for enablingoxidative polymerization of said aromatic compound(s) whereby polymer b)is produced in situ in the form of fine particles or

V) one or more aromatic compounds which are dissolved or dispersed in anorganic solvent in the presence of a polymer b) in the form of fineparticles described above.

Method I of preparing an electrical conductive polymer composition ofthe present invention is described below usingpoly(diallyldimethylammonium-peroxodisulphate), hereafter poly-DDAP, aspolymer b) and unsubstituted pyrrole as the monomeric precursor ofpolymer a), however the process is also applicable to other polymers b)and other monomeric precursors of polymer a).

According to method I dissolved pyrrole is contacted with poly-DDAP inthe form of a coating or a film, which has for example been preparedaccording to method A), B), C) or D) described above. In method I)pyrrole can be dissolved in water or aqueous methanol in an amount offrom 0.1 to 50, preferably of from 1 to 10 weight percent, based on theweight of aqueous methanol. Preferably pyrrole is dissolved in an inertorganic solvent such as propylene carbonate, acetonitrile, a halogenatedhydrocarbon such as methylene chloride or a hydrocarbon such as pentane,hexane or cyclohexane in an amount of from 0.01 to 50 weight percent,preferably from 0.1 to 50 weight percent, more preferably from 1 to 10weight percent, based on the weight of the organic solvent. Preferably,the reaction is performed at a temperature of between 5° and 25° C.,more preferably below ambient temperature. The reaction is spontaneousand is generally completed within about two hours, depending on thethickness of the poly-DDAP film.

The films or coatings produced from poly-DDAP and pyrrole are obtainedin the form of black films or coatings. After having washed the film,for example with methanol and afterwards with water, and after drying,the obtained film-type polymer composition of the present invention ishighly scratch resistent and has good adhesion to substrates such asglass, metal, paper or plastics. Accordingly, the electricallyconductive polymer composition of the present invention is particularlyuseful as a coating. It is preferred to use poly-DDAP as a coating on asubstrate which has been produced according to method A) described abovefor producing these types of electrically conductive polymercompositions. Conductivity measurements of polymer compositions preparedfrom poly-DDAP and pyrrole have shown conductivities between 10⁻⁶ and10⁻⁷ S/cm. Coatings of poly-DDAP have an electrical conductivity ofabout 10⁻¹⁴ S/cm or less when poly-DDAP is dry.

Coatings or films with increased conductivity can be obtained ifconducting salts are added to pyrrole or to the above mentioned aqueousor organic solutions. Preferred conducting salts are those which havebeen previously mentioned above. Inorganic salts in aqueous methanol arepreferred. The volume ratio between water and methanol is in generalfrom about 0.1:1 to about 10:1, preferably from about 0.5:1 to about2:1. If an organic solvent is used for dissolving pyrrole, then organicconducting salts such as alkali and ammonium salts of n-dodecylsulphate,aromatic sulfonic acids, phthalocyanine sulfonic acids, polystyrenesulfonic acids, campher sulfonic acid, styrene sulfonic acid, vinylsulfonic acid, long chain fatty acids or benzene sulfonic acid arepreferably used therewith. These organic conducting salts are soluble inorganic solvents such as acetonitrile, methylene chloride or propylenecarbonate. The organic solvents or aqueous solvents for the conductingsalts such as aqueous methanol may be mixed with the above mentionedsolvents for pyrrole. The molar ratio between pyrrole and the conductingsalt preferably is from 3:1 to 20:1, more preferably from 3:1 to 10:1.Electrically conductive polymer compositions produced from poly-DDAP andpyrrole having an electrical conductivity between about 10⁻² and 10⁻⁴S/cm are obtainable when using conducting salts. The process forproducing electrically conducting polymer compositions in the presenceof conducting salts is particularly suitable for producingself-supporting films. In preparing a self-supporting electricallyconductive polymer composition, it is preferred to start from a self-supporting poly-DDAP film produced according to method B) or D)described above, most preferably according to method B) in which anabove mentioned slightly cross-linked polymeric starting material c) hasbeen used for preparing the poly-DDAP film.

Instead of polymerizing pyrrole in the presence of polymer b) and aconducting salt, it is also possible to produce polymer b), such aspoly-DDAP, in the presence of a conducting salt as described above andthen polymerizing pyrrole in the absence of a conducting salt. Accordingto both methods, polymer compositions are obtainable which have anelectrical conductivity of up to 10⁻² to 10⁻⁴ S/cm.

It has been found that coatings or, preferably, self-supporting films ofthe electrically conductive polymer composition of the present inventionwith even higher electrical conductivities are obtained when a poly-DDAPfilm is used as an anode which is connected with a cathode such as aplatinum electrode. Both electrodes are contacted with an electrolytewhich preferably is an above mentioned organic solvent, optionally mixedwith water, containing an above mentioned conducting salt and pyrrole.Pyrrole and the conducting salt(s) are generally present in theelctrolyte in molar concentrations of from 0.001 to 5. Generally aninitial potential of 1 to 100 volts, preferably of 1 to 50 volts andmost preferably of 2 to 25 volts is applied between the anode and thecathode. According to this method polymer films are obtainable whichhave an electrical conductivity of more than 10⁻² S/cm. These films areuseful as an electrode material or in batteries.

In a further method II) of producing the electrically conductive polymercompositions of the present invention, a film or a coating of polymer b)such as poly-DDAP is contacted with evaporated pyrrole or can be sprayedwith pyrrole.

According to method III of preparing an electrically conductive polymercomposition comprising an electrically conductive polymer a) of one ormore aromatic compounds and a polymer d) having ammonium, phosphonium orsulfonium groups in the polymer chain(s), one uses a polymer b)containing a polydentate, anionic complex which has a redox potentialsufficient for enabling oxidative polymerization of aromatic compounds,such as a substituted or unsubstituted pyrrole, a substituted orunsubstituted thiophene or a substituted or unsubstituted aniline.Polymer b) is used as a solid oxidizing agent. Polymer b) has ammoniumphosphonium or sulfonium groups in the polymer chain(s). Polymer b) isused in the form of fine particles having an average size of 5 nm to 1mm, generally of 10 nm to 0.1 mm, preferably of 100 nm to 0.1 mm andmore preferably of 500 nm to 0.01 mm.

In the following paragraphs method III for preparing an electricallyconductive polymer composition of the present invention, comprising theabove-mentioned polymers a) and d), in an aqueous reaction diluent inthe presence of an above described polymer b) is described in detail.

The aqueous reaction diluent preferably is water. Optionally it containsup to 20 volume percent, preferably only up to 10 volume percentmethanol or an other polar organic liquid, based on the total volume ofthe aqueous reaction diluent.

The useful concentration of polymer b) depends on various factors, suchas the molecular weight of polymer b) and the amount of polar organicliquid which is optionally present. If the aqueous reaction diluentcontains a polar organic liquid in the above mentioned amounts and theaverage weight molecular weight M_(n) of polymer b) is higher than about50,000, diluted dispersions of polymer b) are preferred.

In any event, the amount of polar organic liquid, the molecular weightM_(n) of polymer b) and the concentration of polymer b) in the aqueousreaction diluent should be chosen in such a manner that the reduced formof polymer b), i.e. polymer d), is soluble in the aqueous reactiondiluent.

Polymer b) is dispersed, preferably under vigorous stirring, for exampleat 300 rpm (revolutions per minute) or more, more preferably at 400 rpmto 600 rpm in the aqueous reaction diluent at an amount of 0.01 to 50percent, preferably 0.01 to 40 percent, more preferably of 0.1 to 30percent and most preferably of 0.2 to 20 percent, based on the weight ofthe aqueous reaction diluent. The aqueous dispersion of polymer b)produced according to method G described above without isolation ofpolymer b) can also be used.

The aromatic compound to be polymerized is dissolved or dispersed in theaqueous reaction diluent.

When using heteroaromatic compounds, such as an optionally substitutedpyrrole or an optionally substituted thiophene, the oxidativepolymerization is preferably carried out in the presence of a conductingsalt, for example one of the conducting salts listed above. The aqueousreaction diluent preferably contains the conducting salt in an amount offrom 0.001 to 10 mols per liter, more preferably from 0.01 to 1 mol perliter.

When using an optionally substituted aniline, it is advisable to convertit to its protonated form, i.e., to a salt form, prior to oxidativepolymerization. Preferably, aniline is reacted in situ in the aqueousreaction diluent with one or more inorganic acids, such as HCl, H₂ SO₄or with one or more strong organic acids, such as benzene sulfonic acid,p-toluene sulfonic acid, benzoic acid, CH₃ SO₃ H or trifluoroaceticacid. Benzenesulfonic acid, CH₃ SO₃ H and hydrochloric acid arepreferred. It is not necessary that the entire amount of the protonatedaniline is soluble in the aqueous reaction diluent.

The molar ratio between the aromatic compound to be polymerized and theammonium, phosphonium or sulfonium groups in the cross-linked polymer b)generally is from about 0.01:1 to about 50:1, preferably from about0.1:1 to about 50:1, more preferably from about 1:1 to about 15:1 andmost preferably from about 1:1 to about 5:1.

The useful reaction temperature mainly depends on the type of aromaticcompound to be polymerized. When polymerizing a pyrrole-type aromaticcompound, the reaction temperature should generally be below 25° C. inorder to avoid secondary reactions, such as cross-linking of thepyrrole-type aromatic compound with polymer b), which decrease theelectrical conductivity of the produced polypyrrole; the reactiontemperature preferably is 15° C. or lower, more preferably 5° C. orlower. When polymerizing an aniline-type aromatic compound the reactiontemperature is less critical since aniline is less reactive. Generally,it is from -20° C. to 100° C., preferably from 0° C. to 50° C. and mostpreferably from 5° C. to 40° C.

The color of the reaction mixture changes during the polymerizationprocess. During the polymerization the polydentate anionic complexeshaving the above mentioned redox potential are reduced. The reduced formof polymer b), i.e. polymer d) mentioned above, dissolves in the aqueousreaction diluent.

The dissolved polymer d) which remains in the aqueous reaction diluentcan be reacted with polydentate anionic complexes having the abovementioned redox potential, such as S₂ O₈ ²⁻⁻ groups, as has beendescribed above when describing the preparation of polymer b) frompolymer c). Aqueous solutions which contain S₂ O₈ ²⁻⁻ groups in anamount of more than 1 weight percent, preferably of more than 10 weightpercent, up to saturation are preferably added to the dissolved polymerd). The water-insoluble polymer b) which is produced in such a mannercan be reused in further processes for preparing electrically conductivepolymers a).

The electroconductive polymer composition is obtained in the form offine particles having an average size of 5 nm to 1 mm, generally of 10nm to 0.1 mm, preferably of 100 nm to 0.1 mm, most preferably of 500 nmto 0.01 mm. The polymeric particles can be separated from the aqueousreaction diluent by known means such as conventional filtration,centrifugation or filtration by suction and are preferably purified bywashing, for example with water or organic liquids, such as methanol.

The particles of the electrically conductive polymer composition can bepressed to articles of a stable shape, such as pellets, at a temperaturefrom about 50° C. to about 300° C., preferably from about 100° C. toabout 250° C., and at a pressure of from about 10 bar to about 400 bar,preferably from about 50 bar to about 250 bar, according to the methoddisclosed in DE-A-32 27 914. Generally, the highest measuredconductivities of such pellets are between 10⁻² S/cm and 5 S/cm.

Analysis of the produced electrically conductive material indicates thatthe polymer composition not only contains an electrically conductivepolymer a) but also a polymer d) having ammonium, phosphonium orsulfonium groups in the polymer chain(s). In some cases the presence ofpolymer d) in the produced polymer composition may be due to anincomplete solution of polymer d) in the aqueous reaction diluent.Without wanting to be bound to the theory, it is however believed thatthe particles of the electrically conductive polymer compositionproduced according to method III described above contain a core, whichcontains polymer a) in substantially pure form, and a polymer d) whichis mainly located at the outside of the particles, i.e. polymer d) isthe coating or a partial coating of the particles or acts as asurfactant respectively.

The core/coating structure of the electrically conductive polymerparticles, prepared according to method III, has been confirmed byS.E.M. (scanning electron microscope).

In a further method IV, the monomeric precursor(s) of polymer a) ispolymerized in the presence of one of the above mentioned known polymersc). In this method, a cross-linked polymer b) having anions such as S₂O₈ ²⁻⁻ is produced in situ by polymerizing the monomeric precursor(s) ofpolymer a) in the presence of a water-soluble oxidizing agent whichcontains polydentate anionic complexes having a redox potentialsufficient for enabling oxidative polymerization of the monomericprecursor(s) of polymer a) and in the presence of a polymer c) whichcontains anions which are spontaneously exchangeable with thepolydentate anionic complexes in the water-soluble oxidizing agent.Useful polymers c) and oxidizing agents are described above. Themonomeric precursor of polymer a) such as pyrrole, polymer c) such aspoly(diallyldimethylammonium chloride) and an oxidizing agent such as K₂S₂ O₈ are diluted with a diluting agent such as water or aqueousmethanol, preferably water. The concentration of polymer c) in theaqueous reaction diluent generally is from 0.01 to 50 percent,preferably from 0.01 to 40 percent, more preferably from 0.1 to 30percent and most preferably from 0.2 to 20 percent, based on the weightof the aqueous reaction diluent.

The molar ratio between the monomeric precursor(s) of polymer a) and theoxidizing agent preferably is from 6:1 to 50:1, more preferably from 6:1to 20:1. The ion exchange and the cross-linking of polymer c) and thepolymerization of the monomeric precursor(s) of polymer a) preferably iscarried out in the presence of a conducting salt as described above. Themolar ratio between the monomeric precursor of polymer a) such aspyrrole and the conducting salt preferably is from 3:1 to 20:1, morepreferably from 3:1 to 10:1. According to method IV, polymercompositions of the present invention are preferably produced at atemperature between 15° C. and 40° C., more preferably at about ambienttemperature. The resulting suspension or solution of the electricallyconductive polymer composition of the present invention can be appliedto substrates. After drying, the produced coatings are highly scratchresistant and have a very good adhesion to the substrate. Coatings withan electrical conductivity of up to about 10 -3 S/cm are obtainableaccording to this process.

It has been found that when applying certain reaction conditions inmethod IV, an electrically conductive polymer composition is producedwhich comprises i) a core of an electrically conductive polymer a) ofone or more aromatic compounds and ii) a coating of a polymer d) havingammonium, phosphonium or sulfonium groups in the polymer chain(s), theweight of the coating being up to about 25 percent, based on the totalweight of a) and d) and the polymer composition having an averageparticle size of 5 nm to 1 mm.

Method IV wherein these reaction conditions are applied is describedbelow as method IVa.

The core/coating structure of the electrically conductive polymerparticles prepared according to method IVa is confirmed by S.E.M.(scanning eletron microscope).

In the practice of method IVa, a water-soluble oxidizing agent iscontinuously or batch-wise added to an aqueous reaction mixture whichcontains one or more aromatic compounds, a polymer c) and an aqueousreaction diluent described above. The water-soluble oxidizing agentpreferably is A'₂ S₂ O₈, A'ClO₄, A'₂ Cr₂ O₇, A'MnO₄ or A'₃ [Fe(CN)₆ ]wherein A' is a cation, preferably the hydrogen ion, an alkali metalcation, such as lithium, sodium or potassium, an alkaline earth metalion such as magnesium or calcium or an ammonium ion such as tetramethylammonium or NH₄ ⁺. The most preferred oxidizing agents are H₂ S₂ O₈, Na₂S₂ O₈, K₂ S₂ O₈ and (NH₄)₂ S₂ O₈. Useful aqueous reaction diluents formethod IVa have been indicated above when describing method III forpreparing the electrically conductive polymer composition.

The molar ratio between the ammonium, phosphonium or sulfonium groups inpolymer c) and the oxidatively polymerizable aromatic compoundpreferably is from about 0.001:1 to about 10:1, more preferably fromabout 0.01:1 to about 1:1 and most preferably from about 0.05:1 to about0.5:1. Polymer c) should generally be dissolved in the aqueous reactiondiluent in a concentration of from about 0.01 to about 5 percent,preferably from about 0.1 to about 2.5 percent, based on the weight ofthe aqueous reaction diluent. For obtaining electrically conductivepolymer compositions having a high electrical conductivity, the molarratio between polymer c) and the aromatic compound and the concentrationof the polymer c) in the aqueous reaction diluent is critical. Byvarying the said molar ratio and concentration of polymer c) beyond theabove-mentioned ranges, as described further below, the particle sizeand the electrical conductivity of the produced electrically conductivepolymer composition can be influenced.

When using heteroaromatic compounds, such as an optionally substitutedpyrrole or an optionally substituted thiophene in the oxidativepolymerization process, the aqueous reaction mixture preferably containsan above-mentioned conducting salt. The alkali metal salts such as thesodium salt of benzene sulfonic acid or benzene disulfonic acid, NaHSO₄or CH₃ --SO₃ Na are the most preferred conducting salts. The molar ratiobetween the heteroaromatic compound and the conducting salt preferablyis from about 0.1:1 to about 10:1, more preferably from about 1:1 toabout 4:1.

For the oxidative polymerization of a pyrrole-type aromatic compound areaction temperature of generally about 0 to about 50° C., preferably ofabout 0° to about 20° C., more preferably of about 0° to about 10° C. isuseful. For the oxidative polymerization of an aniline-type aromaticcompound a reaction temperature of generally about 0° to about 80° C.,preferably of about 5° to about 50° C., more preferably of about 15° toabout 40° C. is useful.

The oxidative polymerization process according to method IVa isexplained in detail below using K₂ S₂ O₈ as a water-soluble oxidizingagent although the process is not limited thereto.

In the practice of the oxidative polymerization according to method IVaa catalytic amount of a polymer b) described above containing S₂ O₈ ²⁻groups is produced in situ in an aqueous reaction mixture and isprecipitated from the aqueous reaction mixture by addition of a smallamount of the water-soluble oxidizing agent, such as K₂ S₂ O₈, to theaqueous reaction mixture whereby the S₂ O₈ ²⁻ groups react with polymerc) comprised in the reaction mixture. The produced polymer b) containingS₂ O₈ ²⁻ groups oxidizes the aromatic compounds during their oxidativepolymerization whereby the S₂ O₈ ²⁻ groups in the polymer containingammonium, phosphonium or sulfonium groups are reduced to sulfate groups.The polymer containing ammonium, phosphonium or sulfonium groups andsulfate groups is soluble in the aqueous reaction diluent. Then again asmall amount of the water-soluble oxidizing agent, such as K₂ S₂ O₈, isadded to the aqueous reaction mixture, polymer b) containing S₂ O₈ ²⁻⁻groups is precipitated, etc. until the oxidative polymerization iscompleted. Preferably, aqueous solutions containing from about 0.1weight percent up to saturated solutions of the water-soluble oxidizingagent are added to the aqueous reaction mixture containing an aromaticcompound, polymer c) and optionally a conducting salt. More preferably,the aqueous solution contains from 10 to 70 weight percent of thewater-soluble oxidizing agent. By "water-soluble" is meant that 0.1percent or more, usually 1 percent or more, preferably 10 percent ormore oxidizing agent is soluble in water, based on the water weight. Themolar ratio between the oxidizing agent, such as a peroxodisulfate salt,and the aromatic compound generally is from about 0.1:1 to about 5:1,more preferably from about 0.5:1 to about 2:1, most preferably about1:1.

The oxidizing agent may be continuously added to the reaction mixture,preferably over a time period of from about 4 to about 30 hours, morepreferably from about 6 to about 15 hours. Electrically conductivepolymer powder compositions of surprisingly high conductivities areobtained. Polypyrrole based powder compositions have electricalconductivities of up to 5 S/cm. Polyaniline based powder compositionshave electrical conductivities of up to 25 S/cm.

Alternatively, the oxidizing agent may be added batch-wise to thereaction mixture. Preferably, the total amount of the oxidizing agent isdivided into 5 to 20, more preferably 7 to 15, about equal portions.Preferably, the molar ratio between the added peroxodisulfate ions andthe ammonium, sulfonium or phosphonium groups in the polymer chain(s) ofpolymer c) is not less than about 1:2. It is advisable to stir thereaction mixture for a while after each addition of a portion of theoxidizing agent, preferably from about 15 minutes to about 3 hours, morepreferably from about 30 to about 60 minutes. The produced polypyrrolebased powder compositions have electrical conductivities of up to 5S/cm. Surprisingly, it has been found that polyaniline based powdercompositions having electrical conductivities of even up to 50 S/cm areobtained according to this batch process.

According to method IVa an electrically conductive polymer compositionof a very small particle size, i.e. as low as 10 nm, in same cases evenas low as 5 nm, can be obtained when the molar ratio between theammonium, phosphonium or sulfonium groups in polymer c) and theoxidatively polymerizable aromatic compound, such as an optionallysubstituted aniline, is at least about 25:1, preferably from about 30:1to about 100:1, and the concentration of polymer c) in the aqueousreaction diluent is from about 5 to about 20 percent, preferably fromabout 7 to about 15 percent, based on the weight of the aqueous reactiondiluent.

The produced aqueous dispersion of the electrically conductive polymercomposition comprising polymers a) and d) described above is stable.Upon evaporation of the aqueous reaction diluent mechanically stable,tough films are obtained. Transparent films having a surface resistivityof about 10⁵ to 10⁶ ohms are obtained when producing polyaniline-typepolymer compositions.

When choosing the molar ratio between the ammonium, phosphonium orsulfonium groups in polymer c) and the oxidatively polymerizablearomatic compound of from 5:1 to 10:1 and the concentration of polymerc) in the aqueous reaction diluent is from about 5 to about 20 percent,preferably from about 7 to about 15 percent, based on the weight of theaqueous reaction diluent, abrasion resistant coatings made of theelectrically conducting polymer composition are obtained according tomethod IVa upon evaporation of the aqueous reaction diluent. In the caseof polyaniline-type polymer compositions these coatings have found to benontransparent and having a conductivity of 10⁻² to 10⁻³ S/cm.

The electrically conductive polymer composition produced according tomethod IVa is obtained in the form of particles having an average sizeof 5 nm to 1 mm, usually of 10 nm to 0.1 mm, preferably of 100 nm to 0.1mm and more preferably of 1000 nm to 0.01 mm. The particle coatingconsisting essentially of polymer d) described above which coats atleast a portion of the polymer a) -type core provides a good adhesionbetween the individual particles after the aqueous reaction diluent hasbeen removed. The particles of the electrically conductive polymercomposition can be pressed to articles of a stable shape such as pelletsas described above with respect to the oxidative polymerization processaccording to method III.

Generally the electrically conductive polymer composition of the presentinvention produced in an aqueous reaction diluent according to methodIII or IVa contains up to about 25 percent, preferably from about 2 toabout 20 percent and more preferably from about 5 to about 15 percent ofpolymer d), based on the total weight of the electrically conductivepolymer composition.

In the following paragraphs a fifth method (V) for preparing anelectrically conductive polymer composition of the present invention ofa polymer a) of one or more aromatic compounds and a polymer d) havingammonium, phosphonium or sulfonium groups in the polymer chain(s) in anorganic reaction diluent in the presence of an above described polymerb) is described in detail.

If the organic solvent which is used as a reaction diluent is misciblewith water, the organic reaction diluent may contain water in an amountof less than 80 percent, preferably up to 50 percent, based on the totalvolume of the reaction diluent. Organic reaction diluents which do notcontain substantial amounts of water, for example less than 10 weightpercent, are also useful. When using poly(diallyldimethylammoniumperoxodisulfate) as polymer b), the organic reaction diluent preferablyconsists of a mixture of an organic solvent and water at a volume ratioof about 1:1. In any event, the amount of water has to be small enoughthat a substantial amount of the reduced form of polymer b), i.e. theabove mentioned polymer d), is insoluble in the organic reaction diluentafter the oxidative polymerization process. The suspended fine particlesof polymer d) serve as a carrier or matrix for the produced electricallyconductive polymer a) whereby an electrically conductive polymercomposition is produced. Useful organic solvents are for examplealcohols, such as methanol, ethanol or the propanols; glycols, such aspropylene glycol, ethylene glycol or glycerine; dioxane,tetrahydrofurane, acetonitrile or propylene carbonate.

Polymer b) is dispersed, preferably under vigorous stirring, for exampleat 300 rpm or more, more preferably at 400 rpm to 600 rpm, in theorganic reaction diluent at an amount of 0.01 to 50 percent, preferablyof 0.01 to 40 percent and more preferably of 0.2 to 30 percent, based onthe weight of the organic reaction diluent. An ultrasonic bath is alsouseful for dispersing polymer b) in the organic reaction diluent. Theaqueous dispersion of polymer b) produced according to method Gdescribed above without isolation of polymer b) can also be used andmixed with a sufficient amount of an organic solvent as indicated above.

The aromatic compound, the molar ratio between the aromatic compound tobe polymerized and the cross-linked polymer b) and the useful reactiontemperature are the same as described above with respect to theoxidative polymerization in an aqueous reaction diluent according tomethod III. The oxidative polymerization can be carried out in thepresence of an organic conducting salt. Preferred examples are alkalimetal, alkaline earth metal and ammonium salts of n-dodecylsulfate,aromatic sulfonic acids, phthalocyanine sulfonic acids, polystyrenesulfonic acids, campher sulfonic acid, styrene sulfonic acid, vinylsulfonic acid, long chain fatty acids or benzene sulfonic acid which aresoluble in the organic reaction diluent. The molar ratio between thearomatic compound(s) and the conducting salt preferably is from about3:1 to about 20:1, more preferably from about 3:1 to about 10:1.

The electrically conductive polymer compositions of polymer a) andpolymer d) is obtained in the form of fine particles having an averagesize of 10 nm to 1 mm, preferably of 10 nm to 0.1 mm, more preferably of100 nm to 0.1 mm, most preferably of 500 nm to 0.01 mm. The polymericparticles can be separated from the organic reaction diluent, purified,dried and pressed to articles of a stable shape, such as pellets asdescribed above with respect to the oxidative polymerization processaccording to method III. Generally, the measured conductivities of suchpellets are from 10⁻⁷ S/cm to 5 S/cm.

By oxidative polymerization of the above mentioned aromatic compounds inaqueous or organic reaction diluents according to methods III, IVa andV, electrically conductive, fine polymeric particles having the abovementioned average size are produced. By using polymer b), which isdispersed in the reaction diluent, as an oxidizing agent, electricallyconductive particles of substantially uniform size can be obtained.Furthermore, the produced electrically conductive polymeric particles donot tend to agglomeration to a substantial extent as long as they are inthe aqueous or organic reaction diluent. Without wanting to be bound toa particular theory, it is believed that polymer b) also acts as adispersing agent in the oxidative polymerization process. Electricallyconductive polymeric particles of various sizes can be produceddepending on the chosen process parameters.

The electrically conductive polymer compositions of the presentinvention are useful for many applications generally known forelectrically conductive polypyrrole or polyaniline compositions. Thecoatings or free-standing films can be used as an electrical conductoror semi-conductor, as an electrode material, in a solar cell, for theantistatic finishing of plastics or paper, as an electromagneticshielding material, as an electrochemical membrane, in a heating film,for capacitive scanning or in fuel cells.

The use of the electrically conductive polymer composition as anelectrode material is described below in greater detail. Theelectrically conductive polymer compositions of the present inventionare preferably used for electroplating processes in which organiccompounds are oxidized or reduced. Such organic compounds preferably aremonomeric precursors of polymer a). The electrically conductive polymercomposition preferably is in the form of a coating on a substrate, butself-supporting films are also useful. The polymer composition is usefulas an anode on which a film of an above mentioned polymer a) can bedeposited by electrochemical oxidative polymerization of the monomericprecursor(s) of polymer a). When polypyrrole is deposited on anelectrically conductive polymer composition of the present invention,generally an initial potential of 1 to 100 volts, preferably of 1 to 50volts and most preferably of 2 to 25 volts is applied between the anodeand the cathode. Known cathodes such as platinum electrodes can be usedin conjunction with the aforementioned anodes.

The electrolyte preferably is an organic solvent, optionally mixed withwater, in which conducting salts are quite soluble. Preferred examplesare chlorinated hydrocarbons such as methylene chloride, propylenecarbonate and most preferably acetonitrile. The organic solvents may bemixed with up to 50 weight percent, preferably with up to 25 weightpercent water, based on the weight of the solvent mixture. Usefulconducting salts are the same as those mentioned above. The monomericprecursor(s) of polymer a), such as pyrrole, and the conducting saltsare generally present in the electrolyte in a molar concentration offrom 0.001 to 5. High electrically conductive polymer films having acoating of polymer a) are obtained according to the above describedprocess. These films are useful as electrode materials or in batteries.

The electrically conductive polymer compositions of the presentinvention which have been prepared in the form of granules or a powdercan be used as an electrically conductive filler for a polymer. Theelectroconductive filler can be dispersed in an aqueous or preferably inan organic solution of a polymer, such as a polycarbonate or achlorinated polyethylene. Any polymer is useful which is suitable toform mechanically stable films. The organic solution preferably containsfrom 0.1 to 25 percent, more preferably from 1 to 20 percent of the saidpolymer, based on the weight of the solution. The electroconductivefiller can be used in amounts of 0.1 to 99 percent, preferably of 10 to40 percent, by weight of the polymer. Preferred organic solvents arepolar organic solvents, such as chlorinated solvents, dimethylformamideor tetrahydrofurane. From the produced dispersions films can be preparedby evaporizing the solvent. According to a preferred method thedispersion is applied on a substrate, such as a glass plate beforeevaporizing the solvent.

The above mentioned electroconductive filler can also be blended withthermoplastic polymers by conventional polymer processing methods, suchas using roll-mills or extrusion techniques and the blend can beprocessed to films by known means.

The electrically conductive polymer compositions which have beenprepared according to methods III, IV and V in the form of granules or apowder can also be used for preparing films or coatings. Theelectrically conductive polymer composition of the present invention isdispersed in an aqueous or organic medium. Alternatively, the producedaqueous or organic dispersions containing the electrically conductivepolymer composition of the present invention can be directly usedwithout separating the dispersed electroconductive particles from theaqueous or organic reaction diluent.

In order to obtain films or coating of sufficient mechanical stability,the aqueous or organic dispersion containing the producedelectroconductive particles should also contain a binder for theseelectroconductive particles.

In aqueous dispersions, the dissolved polymer d) which originates fromthe oxidative polymerization process such aspoly(diallyldimethylammonium sulfate) can act as a binder. This is veryadvantageous because the produced aqueous dispersion containing theelectrically conductive polymer composition in the form of dispersedfine particles after the oxidative polymerization can be directly usedfor coating surfaces by simple evaporation of the aqueous reactiondiluent. Other useful binders are water-soluble polymers such ascellulose ethers, for example methylcellulose ethers,hydroxypropylmethylcellulose ethers or carboxymethylcellulose ethers;polyvinylalcohols, poly(vinylalcohol/vinylacetate) and the abovementioned water-soluble polymers c) and polymers d), such aspoly(diallyldimethylammonium) chloride. These polymeric binders can beadded to the aqueous reaction diluent prior to, during or after theoxidative polymerization of the aromatic compounds according to theprocess of the present invention. Alternatively, as mentioned above, theelectrically conductive polymer composition of the present invention canbe separated from the reaction diluent, the wet or dry powder can beredispersed in an aqueous liquid and an above mentioned binder can beadded. The aqueous dispersion preferably contains the polymeric binderat an amount of less than 0 percent, more preferably of 0.1 to 5percent, based on the total weight of the dispersion. The aqueousdispersion is then applied to a substrate, such as wood, paper, glass ora polymeric substrate. After evaporation of the aqueous liquid,conductive or antistatic coatings of various thicknesses and of goodabrasion resistance can be obtained.

Analogously, in organic suspensions thermoplastic organic-solublepolymers are useful as binders.

The electrically conductive polymer compositions produced according toprocesses III and IVa described above wherein polymer a) is anoptionally substituted aniline homo- or copolymer may be deprotonated,for example using an aqueous ammonia solution. These deprotonatedpolymer compositions are soluble in organic solvents such asN-methylpyrrolidone, dimethyl acetamide or dimethyl formamide.Electrically conductive films can be produced from such an organicsolution by casting the solution on a substrate such as a glass plate,evaporizing the organic solvent and treating the film with an acid suchas hydrochloric acid.

The present invention is further illustrated by the following exampleswhich should not be construed to limit the invention. All percentagesand parts are by weight unless otherwise mentioned. Unless otherwisementioned, the electrical conductivity is determined by measuring theelectrical resistivity of powder samples which have been compressed at10 tons to pellets of a diameter of 13 mm and a thickness of 0.1 mm to0.4 mm. The volume resistivity of the pellets and the surfaceresistivity of the coatings and films are measured using a Fluke 8060ARMS multimeter (the distance between the electrodes is one centimeterand the electric potential is 1.18 volt). The values of the volumeresistivity have been found to be dependent on the pressure during themeasurements. The pellets are compressed at 10 kN during themeasurements. Four point-measurements have been carried out according tothe "van der Pauw" method. The electrical conductivity is determined asdescribed by H. J. Mair, S. Roth, "Eletrisch leitende Kunststoffe", CarlHauser Verlag Munchen, Wien, 1986, pages 27-47 and literature citedtherein.

EXAMPLE 1

54.5 g of a 19 percent aqueous solution of poly(diallyldimethylammoniumchloride), hereafter "poly-DADMAC", (0.065 mole), is diluted with waterto a total volume of 250 ml. The poly-DADMAC has a monomer content of 12percent, a polymer content of 88 percent and an intrinsic viscosity of1.71 dl/g.

The solution is slowly added within 2 hours to a solution of 5.81 g(0.025 mole) of (NH₄)₂ S₂ O₈ in 125 ml of water at 10° C. The solutionis vigorously stirred at 500 rpm (revolutions per minute) in order toobtain poly(diallyldimethylammoniumperoxodisulfate), hereafter"poly-DDAP", in the form of an aqueous dispersion (average particle sizeof poly-DDAP as determined by S.E.M.: 0.015 to 0.020 mm).

The residual content of peroxodisulfate dissolved in the aqueoussolution is 0.06 g/l, determined by thiosulfate titration. Thus 98.8percent of the peroxodisulfate has been precipitated from the aqueoussolution.

30 g of aniline (0.32 mole) is brought into a glass reactor andconverted into the hydrochloride form by slowly adding 35 g of 37percent aqueous hydrochloric acid diluted with water to a total volumeof 125 ml. The reactor is purged with nitrogen and heated to 30° C. Theaqueous suspension of poly-DDAP prepared as described above drops intothe reactor within 1 hour. After 1-2 minutes the reaction mixturebecomes dark green. The mixture is stirred for 4 hours at 30° C. aftercomplete addition of the aqueous suspension of poly-DDAP. The product isfiltered by suction, thoroughly washed with water and with littlemethanol. The product is dried in vacuum at 40° C. for 12 hours. 2.2 gof a dark green powder is obtained, the yield is 68 percent, based onthe amount of the peroxodisulfate salt and based on the molecular weightof aniline hydrochloride.

A portion of the powder is pressed to a pellet. The volume resistivityof a 0.3 cm thick pellet is 18 ohms. The surface resistivity of the darkblue metallic glittering pellet is 50 ohms to 80 ohms (two-pointmeasurement).

Analysis data: 58.05 percent C, 5.48 percent H, 5.96 percent Cl, 11.3percent N.

EXAMPLE 2

50 g of the poly-DADMAC solution described in Example 1 is diluted withwater to 500 ml. The solution is dropped into a solution of 45 g (NH₄)₂S₂ O₈ in 500 ml of water. The white precipitate of poly-DDAP is filteredby suction and washed with water (average size of the poly - DDAPparticles as determined by S.E.M. : 0.015 to 0.025 mm). The poly-DDAPpowder is redispersed in 200 ml of water by stirring the suspension for2 hours.

Aniline hydrochloride is prepared in the same manner as described inExample 1. The aqueous poly-DDAP suspension is added to the solution ofaniline hydrochloride and stirred for 18 hours at 30° C. The obtaineddark green particles are filtered by suction, washed with water andlittle methanol. The product is dried in vacuum at 40° C. for 10 hours.2.14 g of a dark green powder is obtained.

The electrical conductivity is determined to be 3.48 S/cm (four pointmeasurement). The particles adhere well to each other in the pellets.S.E.M. pictures show that the particles having a size of 1000 to 2000 nmare bound together in larger agglomerates which have a size of about0.01 mm and are provided with a coating.

EXAMPLE 3

50 g of the poly-DADMAC solution described in Example 1 is diluted withwater to a total volume of 500 ml (0.05 mole, 1.9 percent poly-DADMAC,based on the weight of the solution). This solution is dropped within 2hours under vigorous stirring into a solution of 45 g of (NH₄)₂ S₂ O₈(0.2 mole) in 500 ml of water at a temperature of 10° C. The whiteprecipitate of poly-DDAP is sucked off and washed with water (averagesize of the poly - DDAP particles as determined by S.E.M. : 0.015 to0.025 mm). The precipitate is redispersed in 150 ml of water byvigorously stirring the suspension for 2 hours.

35 g of conc. H₂ SO₄ are cautiously added to 100 ml of water and thereactor is purged with nitrogen. 30 g of aniline (0.32 mole) is addeddrop by drop to the acidic solution. Aniline sulfate precipitates fromthe solution and is dispersed in water by stirring the reaction mixture.The reactor is heated to 30° C. and the aqueous suspension of poly-DDAPis added drop by drop within 25 minutes. After about 2 minutes thereaction mixture becomes dark green. The mixture is stirred for 15 hoursat 30° C. Then the dark green particles are filtered by suction, washedthoroughly with water and with methanol. The product is dried in vacuumfor 12 hours at 40° C. 6.2 g of a dark green powder is obtained. Theelectrical conductivity is determined to be 1.94 S/cm (four-pointmeasurement).

EXAMPLE 4 Preparation of an aqueous suspension of poly-DDAP

50.0 g of a 21.4 percent aqueous solution of poly-DADMAC is diluted withwater to a total volume of 250 ml. The poly-DADMAC has a monomer contentof 7 percent, a polymer content of 93 percent and an intrinsic viscosityof 1.90 dl/g. The solution is added under vigorous stirring to 6.27 g of(NH₄)₂ S₂ O₈ dissolved in 125 ml of water at 5° C. within 1 hour. Theaqueous suspension of the produced poly-DDAP is used for the furtherconversion with aniline.

Preparation of the electrically conductive polyaniline based powdercomposition

54 g of benzene sulfonic acid is dissolved in 500 ml of water in a glassreactor and purged with nitrogen. 30 g of aniline is added drop by dropto the solution and the reactor is heated to 30° C. The aqueoussuspension of poly-DDAP is added within 1 hour. The reaction mixturebecomes dark green and stirring is continued for 15 hours at 30° C. Thenthe polyaniline based powder composition is filtered by suction andwashed with water and methanol. The powder is dried in vacuum for 12hours at 40° C. The yield is 3 g.

A portion of the powder is pressed to a pellet. The volume resistivityof a 0.35 cm thick pellet is 40 ohms (two-point measurement).

EXAMPLE 5

50 g the poly-DADMAC solution described in Example 4 is diluted withwater to a total volume of 500 ml. The solution is slowly dropped into asolution of 63 g of (NH₄)₂ S₂ O₈ in 500 ml of water. The white poly-DDAPprecipitate is filtered by suction and washed with water. The poly-DDAPis dispersed in a mixture of 250 ml of methanol/water (volume ratio 1:1)by vigorously stirring the suspension for 2 hours.

35 g of 37 percent aqueous hydrochloric acid is diluted with water to125 ml in a glass reactor and 125 ml methanol is additionally put intothe reactor. Then 30 g of aniline is slowly added and the reactor isheated to 30° C. The aqueous suspension of poly-DDAP is added drop bydrop within 1 hour. Stirring of the reaction mixture is continued aftercomplete addition of poly-DDAP for 4 hours. The black particles arefiltered by suction and washed with water and methanol. After vacuumdrying at 35° C. for 8 hours 5.9 g of a black powder is obtained.

A portion of the material is pressed into a pellet of 0.35 cm thickness.The volume resistivity is 7 ohms (two-point measurement).

EXAMPLE 6

An aqueous suspension of poly-DDAP is prepared as described in Example2.

50 g NaBF₄ is dissolved in 100 ml of water in a glass reactor which hasbeen purged with nitrogen. 15 g of pyrrole is added to the solution. Thesolution is stirred and heated to 30° C. The aqueous suspension ofpoly-DDAP is added within 1 hour. As soon as the first drops of thesuspension have been added, the reaction mixture becomes dark. Stirringof the mixture is continued for 15 hours at 30° C. Then the blackreaction produced is filtered by suction, washed with water and methanoland dried in vacuum at 35° C. for 8 hours. 13.7 g of a black powder isobtained.

A portion of the material is pressed into a pellet of 0.4 cm thickness.Its volume resistivity is 9.10⁴ ohms.

EXAMPLE 7

Example 7 is carried out as described in Example 6, but the reactiontemperature is kept between 5° C. and 10° C. for 6 hours. The product isisolated, washed and dried as described in Example 6.

The volume resistivity of a pellet of 0.2 cm thickness is 9.10¹ ohms.

EXAMPLE 8

53.3 g of the poly-DADMAC solution described in Example 4 is dilutedwith water to 500 ml and dropped into a solution of 66 g of (NH₄)₂ S₂ O₈in 125 ml of water. The white microflocs of poly-DDAP are filtered,washed with water and again dispersed by stirring them in 150 ml ofwater.

This suspension is dropped into a solution of 54 g benzenesulfonic acidand 20 g pyrrole in a mixture of 450 ml of water and 50 ml of methanolat 5° C. The black reaction mixture is stirred for 5 hours at thistemperature. Then the temperature is allowed to raise to 20° C. andstirring of the mixture is continued for 10 hours. The dark green toblack product of very fine particle size is allowed to settle overnight,the water is then decanted and the particles are isolated by filtration.The product is washed with methanol and dried at 35° C. in vacuum. Theyield of the product is 7.1 g.

The electrical conductivity is determined to be 3.4 S/cm (four-pointmeasurement).

EXAMPLE 9

A suspension of poly-DDAP is prepared as described in Example 2. Thewhite particles are filtered by suction and washed with water. Theproduct is dispersed in 225 ml of a mixture of methanol and water at avolume ratio of 2:1 by vigorous stirring.

225 ml of a mixture of methanol and water at a volume ratio of 2:1 and25 g pyrrole are brought into the glass reactor. The suspension ofpoly-DDAP in the methanol/water mixture is slowly dropped under stirringinto the mixture of pyrrole and the methanol/water mixture. The reactiontemperature is kept at 35° C. for 5 hours. The black product is filteredand thoroughly washed with methanol. After drying in vacuum at 35° C. aportion of the product is pressed into a pellet of 0.15 cm thickness.

Its volume resistivity is 2.10⁶ ohms. The yield is 9.3 g.

EXAMPLE 10

A dispersion of poly-DDAP in 225 ml of a methanol/water mixture,prepared as described in Example 9 is added drop by drop to a solutionof 24.6 g of NaBF₄ in a mixture of 150 ml of methanol, 75 ml of waterand 23 g of pyrrole. The reaction mixture is then stirred for 6 hours.Then the blue-black product is filtered by suction, washed with waterand methanol and dried in vacuum as described in Example 9. The yield ofthe powdery product is 8.5 g.

A 0.2 cm thick pellet of the pressed powder has a volume resistivity of4.10³ ohms.

Use of a polymer composition of polyaniline (polymer b)) andpoly(dimethyldiallylammonium sulfate) (polymer d)) in powder form aselectroconductive filler in a polymer (Examples 11-14) EXAMPLE 11

2.5 g of polycarbonate (sold by Aldrich) is dissolved in 25 ml ofmethylene chloride. 1 g of a pulverized polyaniline based polymercomposition, prepared according to Example 1, is dispersed in thesolution under stirring for 20 hours. A portion of the dispersion isthen poured on a glass plate and the solvent is allowed to evaporate. Aflexible black polycarbonate film of 2 mm thickness is obtained.

The backside of the film which has adhered to the substrate has anelectrical resistivity of 1.10³ ohms to 4.10³ ohms. The resistivity ofthe front surface of the film is about 4.10⁴ ohms.

EXAMPLE 12

2.5 g of polycarbonate is dissolved in 25 ml of methylene chloride and0.25 g of a pulverized polyaniline based polymer composition, preparedaccording to Example 1, is dispersed in the solution. A conductiveantistatic dark-green to black film of 0.2 mm thickness is prepared asdescribed in Example 11.

The backside of the film which has adhered to the substrate has anelectrical resistivity of 10⁴ ohms to 10⁵ ohms; the front surface of thefilm has an electrical resistivity of 10⁶ ohms.

EXAMPLE 13

1 g of a polymer composition which has been prepared as described inExample 5 is dispersed in a solution of 2.5 g of polycarbonate in 25 mlof methylene chloride for 20 hours. A conductive film is prepared asdescribed in Example 11.

The backside of the film which has adhered to the substrate has anelectrical resistivity of 2.10⁴ ohms to 5.10⁴ ohms, the front surface ofthe film has an electrical resistivity of 1.10⁶ ohms to 2.10⁶ ohms.

EXAMPLE 14

52 g of the 21.4 percent poly-DADMAC solution described in Example 4 isdiluted with water to a total volume of 250 ml. This solution is slowlyadded to a solution of 65.2 g of (NH₄)₂ S₂ O₈ in 250 ml of water at 5°C. to 10° C. under vigorous stirring. After stirring for an additionalhour, the white precipitate is filtered and washed with water. The solidpoly-DDAP particles are dispersed in methanol and filtered again. Thisprocedure is repeated with methylene chloride.

30 g of polycarbonate (sold by Aldrich) is dissolved in 300 ml ofmethylene chloride. 200 ml of the solution is placed in a glass reactorand 9 g of aniline hydrochloride prepared according to Example 1 isadded which does not completely dissolve in the solution. The solid,washed poly-DDAP particles are dispersed in 100 ml of the polycarbonatesolution in methylene chloride by vigorous stirring for 2 hours. Somepoly-DDAP is still dispersed in the polymer solution in the shape oflarger flocs. The dispersion is placed into a glass reactor within 1hour while stirring. The reaction mixture becomes blue after about 10 to15 minutes and later black. The reaction mixture is stirred overnight atroom temperature. The dispersion is poured on a glass substrate and thereaction diluent is allowed to evaporate.

The backside of the produced film which has adhered to the glass platehas an electrical resistivity of 2.10³ ohms.

EXAMPLE 15

53.3 g of the 21.4 percent poly-DADMAC solution described in Example 4is diluted with water to a total volume of 250 ml. This solution isdropped under vigorous stirring into a solution of 16.7 g of (NH₄)₂ S₂O₈ in 250 ml of water at 5° C. to 10° C. The white precipitate ofpoly-DDAP is filtered and washed with water. 68.2 g of wet product isobtained.

6.7 g of aniline hydrochloride prepared according to Example 1 isdissolved in 50 ml of water. The wet solid poly-DDAP is added within 4hours in about four parts to the aniline hydrochloride solution at 18°C. After the first part has been added, the reaction mixture becomesblue, then dark-blue and turns to green-black after about 20 minutes.The reaction mixture is stirred for 5 hours and becomes highly viscousdue to the simultaneous formation and dissolution ofpoly(diallyldimethylammonium sulfate) in water. The reaction mixture isdiluted with 50 ml of water and stirring of the solution is continuedfor 15 hours at 20° C. The viscous aqueous dispersion containing thedispersed polyaniline based polymer composition of very fine particlesize is poured on a glass plate. The water is allowed to evaporate. Thedark green to black coating is highly abrasive resistant.

Its electrical resistivity is 1.10³ ohms.

EXAMPLE 16

54 g of the 21.4 percent poly-DADMAC solution described in Example 4 isdiluted with water to a total volume of 500 ml. The solution is slowlyadded to a solution of 6.8 g of (NH₄)₂ S₂ O₈ in 500 ml of water at 5° C.to 10° C. to produce an aqueous dispersion of poly-DDAP.

2.2 g of aniline hydrochloride prepared according to Example 1 is addedto 250 ml of the prepared aqueous dispersion of poly-DDAP at 30° C. Thesolution turns dark green after a couple of minutes. The reactionmixture is stirred for 15 hours at 30° C. The amount of the producedpolyaniline based polymer composition is about 0.2 percent, based on theweight of the aqueous reaction diluent. The aqueous dispersion is pouredon a glass substrate and the water is allowed to evaporate.

The electrical resistivity of the coating is 7.10⁴ ohms.

EXAMPLE 17

200 ml of the aqueous poly-DDAP dispersion prepared according to Example15 is added to 50 ml of an aqueous 2 percent solution of ahydroxypropylmethylcellulose ether. 1.75 g of aniline hydrochlorideprepared according to Example 1 is added and the solution is stirred for15 hours at 30° C. Then the solution is poured on a glass substrate andthe water is allowed to evaporate at 40° C.

The electrical resistivity of the obtained dark green film is 8.10⁵ohms.

EXAMPLE 18

100 g of a 9.5 weight percent aqueous poly-DADMAC-solution (0.06 moleDADMAC, intrinsic viscosity 2.95 dl/g) is acidified by adding 3 drops ofconcentrated hydrochloric acid. 90 mg (0.7 mmole) of anilinehydrochloride is dissolved in this solution. A solution of 160 mg of(NH₄)₂ S₂ O₈ (0.7 mmole) dissolved in 10 ml of water is added drop bydrop (the molar ratio between the ammonium groups in poly-DADMAC and theperoxodisulfate ions or the aniline hydrochloride is 83.7). The solutionis stirred overnight and becomes dark green. The produced polyanilinebased polymer composition is obtained as a microsuspension having aparticle size of about 5 nm. The particles remain dispersed in thereaction diluent, (i.e. do not settle on the bottom of the reactor). Aportion of the solution is brought on a 7×7 cm glass plate and the wateris allowed to evaporate. A dark green light-transmissive coating isobtained which can be peeled off in the form of a flexible, mechanicallystable film having a surface resistivity of 10⁵ ohms.

EXAMPLE 19

Example 18 is repeated, however 90 mg of aniline hydrochloride and 50 mgof pyrrole are added to 100 g of the 9.5 weight percent poly-DADMACsolution mentioned in Example 18. A solution of 180 mg of (NH₄)₂ S₂ O₈dissolved in 10 ml of water is added. Upon evaporation of water alight-transmissive blue to black film is obtained.

EXAMPLE 20

15 g of a 9.5 weight percent aqueous solution of poly-DADMAC (intrinsicviscosity 2.95 dl/g) are diluted with 100 ml of water and 50 ml ofhydrochloric acid. 19.3 g of aniline hydrochloride (0.15 mole) and 1.4 gof pyrrole (0.02 mole) are dissolved in the solution. 36.5 g of (NH₄)₂S₂ O₈ are dissolved in 60 ml of water. The aqueous solution ofperoxodisulfate is slowly but continuously added to the reaction mixturedrop by drop over a period of 6 hours at 5° C. A white precipitate ofpoly-DDAP can be observed at the beginning of the procedure. Thesolution is stirred for 4 hours after addition of the aqueous solutionof (NH₄)₂ S₂ O₈. Then the product is sucked off, washed with 1 m HCllittle methanol and dried in vacuum at 50° C. The yield is 14.3 g. Thevolume resistivity of a 0.23 cm thick pellet is determined to be 8 ohms(two-point measurement). The product can be dissolved inN-methylpyrrolidone after deprotonation with an aqueous ammoniasolution. After evaporation of the solvent, mechanically stable filmsare obtained.

EXAMPLE 21

15 g of a 9.5 weight percent aqueous solution of poly-DADMAC (intrinsicviscosity 2.95 dl/g) are diluted with 150 ml of water and 20 g ofconcentrated hydrochloric acid. A mixture of 10 g of aniline and 1 g ofm-anisidine is slowly added and converted into the hydrochloride form.36.5 g of (NH₄)₂ S₂ O₈ dissolved in 50 ml of water are added to thesolution in portions of 10 ml each. In between, the solution is stirredfor half an hour. After the last addition, the solution is stirred for 2hours. The product is sucked off, washed with 1 m HCl and littlemethanol. The product is dried under vacuum at 50° C. The yield is 13.1g. The volume resistivity of a 0.33 cm thick sample is determined to be12 ohms (two-point measurement). The powder can be dissolved in N-methylpyrrolidone after deprotonation with an aqueous ammonia solution. Amechanically stable film can be casted from the solution.

EXAMPLE 22

20 g of a 9.5 weight percent aqueous solution of poly-DADMAC (intrinsicviscosity 2.95 dl/g) is diluted with 150 ml of water, acidified with 3drops of concentrated hydrochloric acid and brought into a reactor. 13.7g of pyrrole which has been freshly purified over neutral Al₂ O₃ isadded and the solution is stirred. Then a solution of 22 g ofbenzene-1.3-disulphonic acid sodium salt in 50 ml of water is added. Theinitial white precipitate dissolves upon stirring. 45.6 g of (NH₄)₂ S₂O₈ dissolved in 100 ml water of is slowly but continuously added drop bydrop over a period of 8 hours. The temperature is carefully kept between5° and 10° C. The reaction mixture is stirred over night. The blackprecipitate is filtered by suction and washed with water and methanol.The powder is dried at 40° C. for 10 hours under vacuum. The yield is18.5 g. The electrical conductivity is determined to be 0.43 S/cmfour-point measurement).

EXAMPLE 23

Example 22 is repeated. A small portion of the reaction solution isbrought on a 7×7 cm glass plate. The water is allowed to evaporate. Ablack abrasive resistant coating is obtained having an electricalconductivity of 1.10⁻³ S/cm.

EXAMPLE 24

10 g of a 9.5 weight percent aqueous poly-DADMAC solution (0.015 moleDADMAC, intrinsic viscosity 2.95 dl/g) is diluted with 200 ml of water,acidified with 3 drops of concentrated hydrochloric acid and broughtinto a reactor. 50 g (0.4 mole) of aniline hydrochloride are dissolvedin 50 ml of water and added to the reactor. The molar ratio between theammonium groups in poly-DADMAC and the aniline hydrochloride is 0.015:1.45.6 g (0.2 mole) of (NH₄)₂ S₂ O₈ are dissolved in 100 ml of water andadded slowly but continuously within 8 hours to the solution. Thereaction mixture is stirred for 2 hours. The precipitated electricallyconductive polymer composition is sucked off and washed with 1 m aqueoushydrochloric acid. The product is dried under vacuum at 60° C. for 8hours. The yield is 18.9 g (73 percent related to peroxodisulfate andbased on the molecular weight of aniline hydrochloride). The electricalconductivity is determined to be 14 S/cm (four-point measurement).

S.E.M. pictures of the powdery electrically conductive polymercomposition show that the particles have a size of 800 to 1000 nm andthat these particles are bound together in larger aggregates.

EXAMPLE 25

Example 24 is repeated but a molar ratio between the ammonium groups inpoly-DADMAC and aniline hydrochloride of 0.1:1 is selected. Theelectrical conductivity of the precipitated polymer composition whichhas been washed and dried as described in Example 24 is determined to be28.0 S/cm (four-point measurement).

EXAMPLE 26

66.6 g of a 9.5 weight percent aqueous poly-DADMAC solution (0.042 moleDADMAC, having an intrinsic viscosity of 2.95 dl/g) is diluted with 150ml of water and brought into a glass reactor. A solution of 25.9 g ofaniline hydrochloride (0.2 mole) dissolved in 50 ml of water is added.The molar ratio between the ammonium groups in poly-DADMAC and anilinehydrochloride is 0.2:1.45.6 g of (NH₄)₂ S₂ O₈ (0.2 mole) are dissolvedin 100 ml of water. 10 ml of this solution (0.02 mole peroxodisulfate)is added to the reaction mixture at once under vigorous stirring. Thewhite precipitate (poly-DDAP) becomes dark-green within one minute.Stirring is continued for one hour. Additional 10 ml of theperoxodisulfate solution are added to the reactor. The reaction mixtureis stirred for another hour until the next 10 ml portion of NH₄ S₂ O₈ isadded. This procedure is exactly repeated until the perodisulfatesolution is completely consumed. After the last peroxodisulfateaddition, the solution is stirred for another 2 hours. The totalreaction time is about 22 hours.

The fine precipitate is sucked off. The filtered product is washed withlittle methanol and dried over night under vacuum at 60° C. The yield is25.9 g (100 mole percent, based on the amount of peroxodisulfate andaniline hydrochloride). The electrical conductivity is determined to be46.7 S/cm (four-point measurement). S.E.M. photographs of the powdershow the core/coating structure of the polymer particles. Particles ofabout 1000 nm size are agglomerated (bridged) to segmented rods whichare about 0.01 mm long. Due to the polymeric coating there is a goodcontact between the particles.

The powder is deprotonated in an aqueous ammonia solution and dispersedin N-methyl pyrrolidone. Upon evaporation of the solvent, a mechanicallystable film is obtained which can be treated with 1 m hydrochloric acid.

EXAMPLE 27

66 g of a 9.5 weight percent aqueous poly-DADMAC solution (0.041 mole,intrinsic viscosity of 2.95 dl/g) are diluted with 150 ml of water andbrought into a glass reactor. 60 g of a 70 weight percent aqueoussolution of methane sulphonic acid is added. Then 21 g of aniline isslowly added to the reaction mixture upon stirring the solution. 45.6 gof (NH₄)₂ S₂ O₈ (0.2 mole) are dissolved in 100 ml of water. 10 ml ofthe solution (0.02 mole) are added to the reactor at once. The solutionis then stirred for 30 minutes. This procedure is repeated until thetotal amount of the aqueous peroxodisulfate solution is consumed. Thereaction mixture is stirred overnight. The dark blue-green product isfiltered, washed with water and methanol, and dried under vacuum at 50°C. for 15 hours. The electrical conductivity is determined to be 21.4S/cm (four-point measurement).

EXAMPLE 28

1.8 g of a 13.5 percent aqueous solution ofpoly-(diallyldimethylammonium chloride), hereafter designated aspoly-DADMAC is evenly applied to a substrate made of glass having asurface of 7.5 cm×2.5 cm. The poly-DADMAC contains 13 weight percentmonomer and 87 weight percent polymer. The average molecular weight ofpoly-DADMAC is 1,470,000 g/mol, the intrinsic viscosity is 2.16 dl/g.The coated substrate is put in 100 ml of an aqueous solution saturatedwith K₂ S₂ O₈. The poly-DADMAC solution is quickly solidified to a whitefilm. The film is left for two hours in the K₂ S₂ O₈ solution, removedtherefrom and then washed with water and methanol.

The produced film of poly(diallyldimethylammoniumperoxodisulphate),hereafter designated as poly-DDAP, which is fixed on the glass substrateis put in a 5 percent solution of pyrrole in cyclohexane. Polypyrrole isimmediately produced resulting in the film turns black. After threehours the film is removed from the pyrrole/cyclohexane bath togetherwith the glass substrate. Any remaining pyrrole which adheres to thefilm is carefully washed off in methanol. The film is dried at reducedpressure at room temperature. The dried film adheres excellently to theglass substrate and is highly scratch resistant. The specific electricalsurface resistivity of the film is 5.7×10⁶ ohms.

EXAMPLE 29

A film of poly-DDAP on a glass substrate produced according to Example28 is fixed in a glass container near the top which container has beenpurged with nitrogen. The glass container contains liquid pyrrole whichis not in direct contact with the film. A few minutes after thecontainer has been closed, the reaction between the film and the pyrrolegas phase occurs and the polymer film turns black. After two hours thefilm is removed from the container together with the glass substrate andany non-converted pyrrole is removed from the film with methanol and thefilm is dried. The specific electrical surface resistivity of the filmis 5×10⁶ ohms.

EXAMPLE 30

A poly-DDAP film on a glass substrate is prepared as described inExample 28 and fixed in a glass container comprising liquid aniline asdescribed in Example 29. The film and the glass substrate are left forabout 20 hours in the closed container, then removed from the containerand the film is then washed with methanol. The specific electricalsurface resistivity of the film is 3×10⁶ ohms.

EXAMPLE 31

3.2 g of the poly-DADMAC solution of Example 28 is applied to a glasssubstrate and put into a bath containing 35 g of Na₂ S₂ O₈ salt in 120ml of water whereby a solid white film is produced on the substrate.After 2 hours the film and the substrate are removed from the bath andthe film is washed with water. The poly-DDAP film which has beenobtained on the substrate is then put into a bath of 50 ml methanol and100 ml water containing 13.6 g dissolved KHSO₄ and 12 ml dissolvedpyrrole. After 5 hours the film is removed from the bath together withthe glass substrate. The film adheres only partially to the substrate.Any salt adhering to the film is removed with water and the film is thenwashed with methanol.

The specific electrical surface resistivity of the film is 5×10³ ohms(the distance between the electrodes is 1 cm, the potential is 1.15volts). The self-supporting, wet flexible film obtained is resistant towater and organic solvents.

EXAMPLE 32

Example 31 is repeated, however, NaBF₄ is used as a conducting saltinstead of KHSO₄. The specific electrical surface resistivity of thefilm obtained is 4×10³ ohms.

EXAMPLE 33

Example 31 is repeated, however, KPF₆ is used as the conducting saltinstead of KHSO₄. The specific electrical surface resistivity of thefilm obtained is 1×10⁴ ohms.

EXAMPLE 34

A poly-DDAP film on a glass substrate is produced as in Example 31,however a 10 percent aqueous solution of a monomer-free poly-DADMAC isused as a starting material rather than the poly-DADMAC solution used inExample 28. The produced poly-DDAP film on the substrate is placed intoa 5 percent aqueous solution of the sodium salt of polystyrene sulphonicacid to which 8 vol. percent of pyrrole, based on the volume of water,has been added. The film is left in this bath for five hours and removedfrom the glass substrate. The specific electrical surface resistivity ofthe film obtained is 1.6×10³ ohms.

EXAMPLE 35

A poly-DDAP film on a glass substrate is produced as described inExample 34 and is placed into a solution of 12 g of NaBF₄ in 50 ml ofmethanol and 100 ml of water which has been mixed with 10 ml of aniline.The film is left for about 20 hours in the bath and then removed fromthe glass substrate. The specific electrical surface resistivity of thefilm obtained is 2.5×10³ ohms.

EXAMPLE 36

A poly-DDAP film on a glass substrate is produced as in Example 34 andis placed into a solution of 10 g of tetrabutylammonium hydrogensulphatein 100 ml of acetonitrile to which 12 ml of pyrrole has been added.After five hours the film, which adheres strongly to the substrate, isremoved from the solution and then washed with water and then withmethanol. The specific electrical surface resistivity of the filmobtained is 4×10³ ohms.

EXAMPLE 37

80 parts of a 13.5 weight percent aqueous poly-DADMAC solution asdescribed in Example 28 is diluted with 20 parts of water and mixed with6.7 parts of pyrrole. The mixture is stirred for half an hour. 4.1 partsof NaHSO₄ and 4.7 parts of Na₂ S₂ O₈ in 30 parts of water is added whilecooling to 15° C. The solution turns black and highly viscous. Afterhaving stirred for half an hour, a fine dispersion is obtained which isapplied to a glass substrate. After drying, a black, highly adhesive andscratch resistant coating is obtained which has a specific electricalsurface resistivity of 6×10² ohms.

EXAMPLE 38

50 ml of a poly-DADMAC solution is added dropwise to a 30 percentaqueous solution of Na₂ S₂ O₈ under stirring. The poly-DADMAC which isused has a polymer content of 88 percent, a monomer content of 12percent, a viscosity of 3026 cPoise and an intrinsic viscosity of 1.71dl/g. The polymer/peroxo derivative of poly-DADMAC forms quickly as awhite precipitate. Stirring is continued for two hours, the precipitateis filtered off, washed with water and methanol and then completelydried at reduced pressure at ambient temperature.

Elementary analysis data indicates a completely ionically cross-linkedproduct with a residual chlorine content of less than 0.08% (chlorinecontent of poly-DADMAC is 21.95 percent). C:39.74 percent, H:7.57percent, N:5.9 percent, S:13.2 percent, Na:<0.2 percent.

4 parts of poly-DDAP which has been produced according to the processdescribed above but not dried is pulverized and put into a solution of12 parts of NaBF₄ in 100 parts of water. Methanol and pyrrole have beenadded to the water to obtain a volume ratio of water:methanol:pyrrole of100:50:8. The solution is stirred for five hours. The obtained blackmaterial is filtered off, washed with water and then with methanol anddried. The product is pressed to a tablet under a pressure of 10 bar.The specific electrical surface resistivity of the tablet is 3×10³ ohms.

EXAMPLE 39

70 parts of a 65 percent aqueous solution of DADMAC is mixed with 6.3parts of triallylamine and adjusted to a pH of 6 by addition of HCl. Thesolution is heated to 60° C. and mixed with a solution of 0.115 parts of2,2'-azobis-(2-amidinopropane)dihydrochloride, commercially available asWAKO-V-50 in 2 parts of water. The solution is stirred for three hoursat 60° C. and the highly viscous solution is diluted with 70 parts ofwater. An additional 0.10 parts of WAKO-V-50 in 2 parts of water isadded and the solution is stirred for an additional 6 hours at 60° C.

After cooling, 6.5 g of the highly viscous reaction product is appliedto a glass plate of 7.5 cm×7.5 cm and left for two days. The film, whichis formed after evaporation of the water, is removed from the glassplate. It has a good mechanical stability. The film has a thickness of0.5 to 0.7 mm and is put into a 30 percent aqueous Na₂ S₂ O₈ solution.After two hours, the originally colorless film has become white and noportions of the film have been dissolved in the solution. The film isremoved from the bath and washed with water and then with methanol.

The film is put in a suspension of 16 g of the sodium salt of p-styrenesulphonic acid in 100 ml of acetonitrile and 12 ml of pyrrole. After 10hours a deeply black, wet film of extraordinary stability is obtained.The film is washed with methanol. The specific electrical surfaceresistivity of the film obtained is 5×10³ ohms.

EXAMPLE 40

2 g of poly(2-vinylpyridine) is dissolved in 5 ml of a 16 percentsolution of HCl in water and converted to the hydro-chloride form. Theviscous solution is applied to a glass substrate of 7.5 cm×2.5 cm. Theglass substrate coated with poly-(2-vinylpyridiniumhydrochloride) is putinto 100 ml of a saturated solution of potassium peroxodisulphate inwater.

After 15 minutes, the glass substrate having a sticky coating ofpoly(2-vinylpyridiniumperoxodisulphate) which adheres well to thesubstrate is washed with water and methanol and then put into a bath ofcyclohexane containing 5 percent of pyrrole. The film turns blackquickly. The coated glass substrate is removed from the bath after 15minutes and washed with methanol. The specific electrical surfaceresistivity of the film obtained is 2×10⁴ ohms.

EXAMPLE 41

6 parts of a 4-vinylpyridine/styrene copolymer, having a styrene contentof 10 percent, which is commercially available from Aldrich is dissolvedin 35 parts of a 16 weight percent solution of HCl in water andconverted to the hydrochloride form. The highly viscous solution isapplied to a glass substrate and put into a 20 weight percent aqueoussolution of (NH₄)₂ S₂ O₈. The polymer solution is immediately solidifiedinto a white film. The glass substrate containing the film which adheresvery well to the substrate is washed with water and methanol and thenput into a bath of 100 ml of acetonitrile containing 12 g of NaBF₄ and 5ml of pyrrole. The substrate containing the film is removed from thebath after 2 hours and washed with methanol. The specific electricalsurface resistivity of the scratch resistant dry coating obtained isbetween 10³ and 10⁴ ohms.

EXAMPLE 42

6 parts of a 4-vinylpyridine/styrene copolymer, having a styrene contentof 10 percent, which is commercially available from Aldrich is dissolvedin 35 parts of a 16 weight percent solution of HCl in water andconverted to the hydrochloride form. The highly viscous solution isapplied to a glass substrate. The water is allowed to evaporate and acoating is obtained. The glass substrate containing the coating whichadheres very well to the substrate is put in a 10 weight percent aqueoussolution of (NH₄)₂ S₂ O₈. After 2 hours the transparent coating has beenconverted to a white tough, sticky material and no portions of thecoating have been dissolved in the solution. The substrate containingthe coating is put into a bath of a mixture of 100 ml of water and 50 mlof methanol containing 6.8 g of sodium dodecylhydrogensulfate and 6 mlof pyrrole. The polymer/peroxo-coating gradually becomes black afterabout 10 minutes. The substrate containing the black coating is removedfrom the bath after 5 hours. The coating can be pulled off the substratein form of a film. The wet film is mechanically stable and flexible buttends to become somewhat brittle when completely dried. The surface ofthe film which has been exposed to the pyrrole/sodiumdodecylhydrogensulfate solution is black and mat and has an electricalresistivity of about 10³ ohms. The back side of the film which hasadhered to the substrate is black and glossy and has an electricalresistivity of 10⁶ ohms due to the fact that only pyrrole and not thebulky dodecylhydrogensulfate anion could penetrate the film.

EXAMPLE 43

5 parts of the 4-vinylpyridine/styrene copolymer described in Example 41is dissolved in 100 parts of a 10 weight percent aqueous solution ofHBF₄. The highly viscous solution is applied to a glass substrate andput into a 10 weight percent solution of (NH₄)₂ S₂ O₈. The polymersolution is solidified into a white film. The glass substrate containingthe film is washed with water and put into a mixture or 100 ml ofmethanol and 60 ml of a 10 weight percent aqueous solution of HBF₄containing 6 g of aniline. The substrate containing the black coating isremoved from the mixture after 2 hours and washed with water andmethanol. The specific electrical surface resistivity of the coating is10³ ohms.

EXAMPLE 44

4 g of a copolymer produced from 50 mol percent DADMAC and 50 molpercent acrylamide (80 percent DADMAC conversion, molecular weight about3,000,000) is dissolved in 200 ml of water. 25 ml of a 20 weight percentaqueous (NH₄)₂ S₂ O₈ solution is added at once to the stirred polymersolution. The polymer-peroxo derivative immediately precipitates fromthe solution in the form of a white gel-like material. 500 ml of acetoneis added to the solution in order to complete the polymer precipitation.The product is separated by filtration and washed with 2×100 ml ofacetone and additionally with 100 ml of acetonitrile. 8.6 g of the wetproduct is put into a solution of 5.4 g of NaBF₄ and 5 ml of pyrrole in50 ml of acetonitrile. The polymerperoxo derivative gradually turnsblack within 40 minutes. The product is washed with methanol, dried andpressed to a tablet. The specific electrical surface resistivity of thetablet is 4×10⁴ ohms.

EXAMPLE 45 Preparation of poly. (p-xylylene-a-dimethylsulfoniumchloride.).

a) Production of the monomer

The production of a compound of the formula ##STR5##(p-xylylene-α-dimethylsulfonium chloride) and its polymerization areknown. 13.1 g of p-xylylene dichloride and 55 ml of dimethylsulfide areheated overnight to 55° C. in 100 ml of methanol. The solvent isremoved. 50 ml of acetone is added. Upon removal of the solvent,crystalline xylylene-α-dimethylsulfonium chloride is obtained which isdried at 40° C. under vacuum.

b) Polymerization

15 g of xylylene-α-dimethylsulfonium chloride is added to 150 ml ofwater and cooled to 0° C. 2.6 g of NaOH in 150 ml of water at atemperature of 0° C. are added within 5 minutes. The reaction mixturebecomes viscous after 5 to 10 minutes. After 1 hour at 0° C., thereaction mixture is quenched with 15 ml of concentrated HCl.

Preparation of an electrically conductive film

0.6 g of a purified aqueous 10 wt.% solution of poly(p-xylylene-α-dimethylsulfonium chloride) is evenly applied to asubstrate made of glass having a surface of 7.5 cm×2.5 cm. The coatedsubstrate is put in 100 ml of an aqueous 10 wt. % solution of (NH₄)₂ S₂O₈. The polyelectrolyte is quickly solidified to a white film. The filmis left for 15 minutes in the peroxydisulfate solution, removedtherefrom and washed with water.

The produced polymeric peroxydisulfate is put in a bath of 10.5 g ofbenzene sulphonic acid, 2.4 g NaOH, 50 ml of water, 25 ml of methanoland 25 ml of ethanol to which 10 g of pyrrole is added. The film turnsblack immediately. After 20 minutes the film is removed from the bathand washed with methanol. The solvent is allowed to evaporate. Thesurface resistivity of the dried film which shows a good adherence tothe glass surface is 5×10² ohms.

The dry coated substrate is put on a metallic plate which has beenpretreated to 100° C. The temperature is kept for 3 minutes. The blackfilm turns partially blue. Its surface resistivity is 7×10² ohms atroom-temperature. The coating is resistant to water and organicsolvents.

EXAMPLE 46

A film of the polymeric peroxydisulfate prepared as described in Example45 is fixed in a glass container near the top. The glass containercontains liquid pyrrole which is not in direct contact with the film. Afew minutes after the container has been closed, the reaction betweenthe film and the pyrrole gas phase occurs and the polymer film turnsblack. After 5 hours the film is removed from the container togetherwith the glass substrate and the film is dipped in a wash solution ofmethanol/water 1:1. Then the wet film together with the substrate is puton a heater of 95° C. and left for about 5 minutes. The dry grey-blackcoating has a surface resistivity of 2×10⁴ ohms.

EXAMPLE 47

A balck but wet polypyrrole/polyelectrolyte coated substrate prepared asdescribed in Example 45 is put on a heating plate. The plate is heatedto 100° C. and the coating is left there for about 3 minutes until thecolor of the coating turns dark blue. The surface resistivity of thecoated substrate is 8×10² ohms at room temperature.

EXAMPLE 48

A film of polymeric peroxydisulfate prepared as described in Example 45is put in 10 wt. % aqueous solution of aniline hydrochloride. The filmturns dark after a few minutes. The film and the substrate are removedfrom the bath after 15 minutes, dipped in a wash-water solution andheated to 95° C. on a metallic heating plate. After dimethylsulfide hasbeen split off, a green-yellow coating having a surface resistivity of1×10³ ohms at room temperature is obtained.

EXAMPLE 49 Use of a coating prepared from poly-DDAP and pyrrole as anelectrode material

The scratch resistant and abrasive resistant coating prepared frompoly-DDAP and pyrrole on a glass substrate of 7.5 cm×2.5 cm producedaccording to Example 28 is used as an anode. A platinum electrode of 2cm×4 cm and 0.1 mm thickness is used as a cathode. The electrolyteconsists of a 0.1 molar solution of tetrabutylammoniumtetrafluoroboratein 100 ml of acetonitrile which additionally contains pyrrole at aconcentration of 1 molar. The electrodes are located in a closedcontainer used for electrolysis at a distance of about 2.5 cm. Theportion of the surface of the electrodes which is dipped into thesolution is about 2 cm×2.5 cm. A potential of 20 volts is applied forabout 41/2 hours. The coated substrate is taken out of the bath, washedwith methanol and dried under reduced pressure at ambient temperature.The electrical surface resistivity of the coating which has not been indirect contact with the electrolyte is 9×10⁴ ohms. The surface of thecoating which has been located in the electrolyte is coated with a layerof anodically deposited polypyrrole, its electrical surface resistivitybeing 140 ohms. This portion of the coating can be removed from thesubstrate as a thin, black, mechanically stable, flexible film.

COMPARATIVE EXAMPLE

Example 49 is repeated, however a platinum electrode is used as an anodeinstead of a glass substrate coated with the coating produced frompoly-DDAP and pyrrole. A second platinum electrode, which has beendescribed in Example 49, is used as a cathode. The distance between thetwo electrodes and the type of electrolyte solution are the same as inExample 49. The electrochemical deposition of pyrrole (concentration 1molar) is carried out at a potential of 1.5 volts. After one hour, aportion of the platinum electrode is coated with a black film ofpolypyrrole. After an additional hour, the platinum electrode is removedfrom the bath and any conducting salt which still adheres to thedeposited polypyrrole is removed with methanol. The coated electrode isthen dried. It has an electrical surface resistivity of 32 ohms. It isnot possible to remove polypyrrole produced under these conditions fromthe electrode in the form of a self-supporting film.

EXAMPLE 50

The mechanically stable wet poly-DDAP film prepared from poly-DADMAC andNa₂ S₂ O₈ according to Example 39 is used as an anode. A platinumelectrode as described in Example 49 is used as an cathode. Theelectrolysis is carried out as described in Example 49, but 300 ml ofacetonitril containing tetrabutylammoniumtetrafluoroborate at aconcentration of 0.1 molar and pyrrole at a concentration of 0.5 molaris used as an electrolyte. As soon as the poly-DDAP film is dipped intothe bath, it becomes black and conductive. The film is switched as ananode and a voltage of 4.5 volt is applied for about 10 minutes. Thevoltage is then decreased to 2.2 volt for 1.5 hours. The electricalconductivity of the film is 0.7 S/cm (measured by four-pointmeasurement).

I claim:
 1. Electrically conductive polymer particles having an averagesize of 5 nm to 1 mm and comprisingi) a core of an electricallyconductive polymer a) containing one or more oxidatively polymerizablearomatic compounds and ii) a coating of a polymer d) having ammonium,phosphonium or sulfonium groups in the polymer chain(s),wherein theweight of the coating is up to about 25 percent, based on the totalweight of a) and d).
 2. The polymer particles of claim 1 wherein theoxidatively polymerizable aromatic compound in polymer a) is selectedfrom the group consisting of pyrroles, thiophenes and anilines.
 3. Thepolymer particles of claim 1 wherein polymer d) is a homo- or copolymerof one or more monomers of Formula I ##STR6## wherein A and B are thesame or different and represent a C₁₋₁₂ -- alkyl or phenyl radical,either unsubstituted or having one or more substituents which are notpolymerizable in the presence of a free radical initiator; or A and Btogether represent --CH₂ --CH₂ --CH(CH₃)--CH(CH₃)--, --CH═CH--CH═CH--,--CH═CH--CH═N--, or --CH═CH--N═CH--; andR and R' are the same ordifferent and represent hydrogen, unsubstituted C₁₋₆ -alkyl,unsubstituted phenyl, nitro-C₁₋₆ -alkyl, substituted C₁₋₆ -alkyl orsubstituted phenyl, the substituents being selected from the group ofhydroxy, amido, loweralkoxyl, phenoxy, naphthoxy, cyano,thioloweralkoxy, thiophenoxy, loweralkoyl and 5- or 6-memberedcycloalkyl.
 4. The polymer particles of claim 3 wherein A and B inFormula I each independently represent methyl, ethyl or unsubstitutedphenyl and R and R' independently are hydrogen or methyl.
 5. The polymerparticles of claim 4 wherein A and B in Formula I represent methyl and Rand R' independently are hydrogen or methyl.
 6. The polymer particles ofclaim 1 wherein the aromatic compound is a substituted or unsubstitutedaniline.
 7. The polymer particles of claim 1 wherein the aromaticcompound is selected from the group of thiophenes and pyrroles.
 8. Thepolymer particles of claim 1 wherein the particles have an average sizeof 10 nm to 0.1 mm.
 9. A polymer composition comprising a polycarbonateor chlorinated polyethylene and, as a filler, electrically conductivepolymer particles having an average size of 5 nm to 1 mm andcomprisingi) a core of an electrically conductive polymer a) containingone or more oxidatively polymerizable aromatic compounds and ii) acoating of a polymer d) having ammonium, phosphonium or sulfonium groupsin the polymer chain(s), wherein the weight of the coating is up toabout 25 percent, based on the total weight of a) and d).
 10. Thepolymer particles of claim 1, wherein polymer d) contains sulfate groupsas counter-ions.